Solution compositions of organo-silicone polymers

ABSTRACT

SOLUTION COMPOSITIONS ARE PROVIDED CONSISTING ESSENTIALLY OF FOUR DIFFERENT INGREDIENTS: (1) A LIQUID ORGANOSILICONE POLYMER CONTAINING MONOMERIC UNITS (A), (B) AND (C) WHERE A IS SIO4/2, B IS A POLYFUNCTIONAL SILOXY UNIT IN WHICH SILICON IS BONDED TO AT LEAST ONE ORGANIC MOIETY BEARING A POLY(OXYALKYLENE) CHAIN, AND C IS A MONOFUNCTIOAL TRIORGANOSILOXY CONSISTING ESSENTIALLY OF ONE OR (B) TO (C) BEING 0.4-2:1:0.2-2, RESPECTIVELY; (2) AN ORGANIC ACIDIC COMPONENT CONSISTING ESSENTIALLY OF ONE OR MORE ALIPHATIC AND CYCLOALIPHATIC CARBOXYLIC ACIDS HAVING 15-20 CARBON ATOMS; (3) A NON IONIC ORGANIC SURFACTANT; AND (4) A WATER SOLUBLE GLYCOL. THE SOLUTION COMPOSITIONS ARE USEFUL AS SURFACTANT-PROVIDING COMPOSITIONS FINDING PARTICULAR APPLICATION IN THE MANUFACTURE OF FLEXIBLE POLYESTER URETHANE CELLULAR PRODUCTS, INCLUDING FLAME-RETARDED FOAMS.

United States Patent US. Cl. 252-356 9 Claims ABSTRACT OF THE DISCLOSURESolution compositions are provided consisting essentially of fourdifferent ingredients: (1) a liquid organosilicone polymer containingmonomeric units (A), (B) and (C) where A is SiO B is a polyfunctionalsiloxy unit in which silicon is bonded to at least one organic moietybearing a poly(oxyalkylene) chain, and C is a monofunctionaltriorganosiloxy unit, the mole ratio of (A) to (B) to (C) being0.42:1:0.22, respectively; (2) an organic acidic component consistingessentially of one or more aliphatic and cycloaliphatic carboxylic acidshaving -20 carbon atoms; (3) a non ionic organic surfactant; and (4) awater soluble glycol. The solution compositions are useful assurfactant-providing compositions finding particular application in themanufacture of flexible polyester urethane cellular products, includingflame-retarded foams.

BACKGROUND OF THE INVENTION The present invention relates to novelorganosilicone polymers, and their use in the manufacture of urethanecellular products, particularly flexible polyester urethane foamsincluding flame-retarded foams.

It is well known that the urethane linkages of urethane foams are formedby the exothermic reaction of a polyfunctional isocyanate and apolyfunctional active hydrogen-containing compound in the presence of acatalyst, and that the cellular structure of the foam is provided by gasevolution and expansion during the urethane-forming reaction. Inaccordance with the one-shot process which is the most widely usedindustrial technique, direct reaction is effected between all of the rawmaterials which include the polyisocyanate, the activehydrogen-containing compound, the catalyst system, blowing agent andsurfactant. A major function of the surfactant is to stabilize theurethane foam, that is, prevent collapse of the foam until the foamedproduct has developed sufficient gel strength to become self-supporting.

It is also Well known that suitable active hydrogencontaining compoundsinclude polyether polyols and polyester polyols. From the standpoint oftheir chemical structure, therefore, urethanes are usually classified aspolyether and polyester urethanes, respectively. Urethane foams alsodiffer with respect to their physical structure and, from thisstandpoint, are generally classified as flexible, semi-flexible or rigidfoams.

Although certain techniques of urethane manufacture such as the one-shotprocess and certain components of the foam formulation such as thepolyisocyanates, amine catalyst and blowing agent, are generally useful,a specific problem associated with the production of a particular typeof urethane foam and the solution thereto are often peculiar to theparticular chemical and physical structure of the desired foamedproduct. Thus, a significant developmcnt in the production of apolyether foam or a rigid foam, for example, may not be generallyapplicable to the production of other cellular products. In particular,the eflicacy of the foam stabilizer is usually selective with icerespect to the formation of a particular type of foam. For example,although flexible polyester foam was originally made using conventionalorganic surfactants or emulsitiers, such compounds were not effectivefor the manufacture of flexible polyether foam. As urethane technologyadvanced and end-uses became more varied, it became apparent thatcertain deficiencies in the quality of flexible polyester foam such asthe presence of splits and a nonuniform cell structure wereattributable, at least in part, to the organic surfactants employed.However, the mere substitution of the organic surfactants with variouspolysiloxane-polyoxyalkylene block copolymers which had been used asfoam stabilizers with satisfactory results in the production of othertypes of urethane foams (e.g., in the production of polyether urethanefoams and certain rigid polyester urethane foams), did not producecompletely satisfactory flexible polyester foams. A significantdevelopment in polyester foam manufacture was the dis covery that asatisfactory combination of uniform cell structure and freedom fromsplits was achieved by using a particular combination of foamstabilizing ingredients. This latter combination comprises (a) ananionic organic surfactant that is soluble in the polyester polyolreactant at room temperature and that is capable of lowering the surfacetension of the polyester resin reactant when dissolved therein and (b) apolysiloxane-polyoxyalkylene block copolymer surfactant characterized bya particular molecular weight (from 600 to 17,000), siloxane content(from 14 to 40 weight percent based on the weight of the copolymer) andoxyethylene content (at least weight percent based on the total amountof oxyalkylene groups in the copolymer). This particular advance inpolyester foam manufacture is described in greater detail in BelgianPatent No. 724,951 corresponding to US. Application Ser. No. 68 8,702,filed Dec. 7, 1967, by Lawrence Marlin, now US. Pat. No. 3,594,334.

Another class of organosilicone polymers known to the art are thosecomposed of the following two types of silicon-containing units: (1)inorganic tetrafunctional units in which the four valences of siliconare bonded to oxygen (SiO and (2) the monofunctional trimethylsiloxyunits, (CH SiO Polymers of this type in which the SiO :(CH SiO moleratio is from 0.8:1 to 20:1 are described in Belgian Pat. No. 720,212 aseffective stabilizers of flexible polyether urethane foams. On the otherhand, copolymers composed of the aforesaid SiO and (CH SiO units areineffective stabilizers of flexible polyester foam.

Also reported in the prior art (US. Pat. No. 3,511,788) are polymerscontaining the aforesaid inorganic tetrafunctional units in combinationwith (CH SiO units either as the sole type of monofunctional unit or infurther combination with a second type of monofunctional unit in whichthe silicon atom is bonded to two methyl groups and ahydroxyl-terminated poly(oxyalkylene) chain which is linked to thesilicon atom by a divalent trimethylene group. In the polymers of US.Pat. 3,511,788, the proportion of tetrato total mono-functional unitsranges from 110.6 to 111.2. Although the polymers of the aforesaidpatent are reported therein as useful frothing agents in the manufactureof polyvinyl chloride plastisol foams and foaming agents for simpleorganic solvents, they are inefiective stabilizers of flexible polyesterfoam.

An additional factor which further complicates this area of technologyis the need to minimize and ultimately overcome the major drawback ofurethane foams in their ability to ignite readily and to burn. In viewof the fact that urethane foams are used in applications where firecreates a hazard, a great deal of effort has been and is being expendedto impart and improve their flame-retardant properties. Here too,however, specific types of foams have selective requirements.Flame-retardancy is particularly difficult in the area of flexible foammanufacture in view of the delicate open-cell nature of flexible foamsas compared with the closed-cell and highly cross-linked rigid foams.The problem is compounded by the desirability of achievingfire-retardant properties without any substantial sacrifice of foamquality required for a particular end-use application.

It is an object of this invention to provide new and usefulorganosilicone polymers which have particular application in themanufacture of cellular polyurethanes.

Another object is to provide new and improved organosilicone polymerswhich as such are potent stabilizers of flexible polyester urethane foamincluding flame-retarded foam.

Another object is to provide organosilicone polymers having theaforesaid characteristics, in a form which results in clear, homogeneoussolutions when premixed with water and an amine urethane-formingcatalyst.

A further object is to provide organosilicone polymers containinginorganic, tetrafunctional silicon-containing units as one type ofmonomeric unit, which polymers are effective stabilizers of flexiblepolyester urethane foam, and a method for the preparation of saidpolymers.

A further object is to provide particular flexible polyester urethanecellular products having fire-resistant properties, and a process forthe manufacture thereof.

Various other objects and advantages of this invention will becomeapparent to those skilled in the art from the accompanying descriptionand disclosure.

SUMMARY OF THE INVENTION In accordance with the teachings of thisinvention, organosilicone polymers are provided which comprise: (A)inorganic, tetrafunctional silicon-containing units in which the fourvalences of the respective silicon atoms are satisfied by bonds tooxygen, (B) polyfunctional siloxy units in which silicon is bonded to atleast one organic moiety bearing a poly(oxyalkylene) chain, and (C)monofunctional triorganosiloxy units, and in which the mole ratio ofsaid tetrafunctional to said polyfunctional units is from about 0.4:1 toabout 2:1 and the mole ratio of said monofunctional to saidpolyfunctional units is from about 0.2: l to about 2:1.

For convenience, the aforesaid monomeric units of the polymers of thisinvention are referred to herein generally as the A, B and C units,respectively.

In addition to the aforesaid novel class of organosilicone polymers, thepresent invention also provides a process for producing a flexiblepolyurethane foam which comprises reacting and foaming a reactionmixture of:

(I) a polyester polyol containing an average of at least two hydroxylgroups per molecule;

(II) a polyisocyanate containing at least two isocyanato groups permolecule, said polyester polyol and polyisocyanate, taken together,being present in the mixture in a major amount and said polyester polyoland polyisocyanate being present in the mixture in the relative amountsrequired to produce the polyurethane foam;

(III) a blowing agent in a minor amount sufiicient to foam the mixture;

(IV) a catalytic amount of a catalyst for the reaction of the polyesterpolyol and the polyisocyanate to produce the polyurethane; and

(V) a foam stabilizing amount of the organosilicone polymers of thisinvention comprising the aforesaid tetrafunctional, organo-substitutedpolyfunctional and monofunctional silicon-containing units A, B and C.

The organosilicone polymers of this invention can be introduced to theurethane foam-producing reaction mixture either as such, as a blend withvarious organic additives, or as a component of an aqueous premixturewhich also comprises the catalyst for the polyesterpolyol/polyisocyanate reaction.

In addition to their effectiveness for stabilization of flexiblepolyester foam, the organosilicone polymers of this invention have thefurther advantageous property of allowing for the formation offlame-retarded foams.

The present invention also relates to methods for the preparation of thenovel organosilicone polymers described herein, particular solutioncompositions thereof, and to the foams which are made therewith.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The functionality of therespective types of structural units (A, B and C) of the polymers ofthis invention defines the number of oxygen atoms to which the siliconatom (Si) of any particular unit is bonded. Since each oxygen atom isshared by a silicon atom (Si) of another unit, functionality alsodenotes the number of linkages by which the particular unit can bebonded to another portion of the polymer through Si- OSi bonds.Accordingly, in expressing the structural and empirical formulas of therespective units of the polymers of this invention, fractionalsubscripts are used in which the value of the numerator definesfunctionality (i.e., the number of oxygen atoms associated with thesilicon atom of the particular unit), and the denominator, which in eachinstance is 2, denotes that each oxygen atom is shared with anothersilicon atom.

Thus, in the inorganic tetrafunctional units (A) of the polymers of thisinvention, each of the four valences of silicon is associated withoxygen as shown by the structure,

I and expressed by the empirical formula, SiO which in abbreviated formis often expressed simply as SiO In the organo-substitutedpolyfunctional structural units (B) of the polymers of this invention,from two to three valences of the tetravalent silicon atom areassociated with oxygen and at least one valence is satisfied by a bondto a carbon atom of an organic moiety bearing a poly- (oxyalkylene)chain. For the sake of brevity, the said poly(oxyalkylene) chain-bearingorganic moiety is also referred to herein as the polyether group and isdesignated herein by the symbol E. When the B unit is difunctional, theremaining valence of silicon is satisfied by a bond to a carbon atom ofeither a second polyether group (E) or a monovalent hydrocarbon radical,designated herein by the symbol R. Consistent with this definition, thepolyfunctional siloxy units (B) of the polymers of this invention havethe following general struc tural formula:

wherein E is the aforesaid poly(oxyalkylene) chain-bearmg organic moiety(i.e., a polyether group), R is a monovalent hydrocarbon radical, e isan integer having a value of from 1 to 2, f has a value of from 0 to l,and the sum e-l-f is from 1 to 2.

When the sum e+f of general Formula B is 2, the polyfunctional siloxyunits (B) of the polymers of this invention are difunctional and havethe structural formula,

Rr i/2-Ti0i/2-, EB and the empirical formula,

)e( )liO2/7r which in abbreviated form is expressed as wherein f has avalue of one when e is one, and f is zero when e is two. Formulas B andB-1, therefore, include both the mono(polyether)-substituted and thedi(polyether) -substituted difunctional units, (E) (R)SiO and E SiOrespectively.

When the sum e +f of general Formula B is 1, the polyfunctional siloxyunits (B) are trifunctional and have the structural formula,

and the empirical formula, ESiO In view of their polyfunctionality, thethree types of B units encompassed by general Formula B have the commoncharacteristics of being polymer-building units. It is to be understoodthat the organosilicone polymers of this invention may contain eitherone of the two types of difunctional structures encompassed by FormulaB-l [that is, (R) (E)SiO or E SiO or the trifunctional structure ofFormula B-2 (that is, ESiO as essentially the sole type ofpolyfunctional unit (B), or the polymers may contain any combinationthereof such as, for example, a combination of the (R) (E)SiO and ESiOmonomeric units.

In the monofunctional siloxy units (C) of the polymers of thisinvention, one valence of silicon is associated with oxygen and each ofthe remaining three valences is satisfied by a bond to a carbon atom ofa monovalent organic group, designated herein as R, as shown by thegeneral structural formula,

which has the empirical formula, R SiO The R group can be a monovalenthydrocarbon group, designated herein as R, or the R group can be apoly(oxyalkylene) chain-bearing organic moiety, also referred to hereinas a polyether group and designated by the symbol E. Within anyparticular R SiO unit, or, as between different R SiO units, the Rgroups may be the same or different. Thus in the monofunctional units(C), from 0 to 3 monovalent hydrocarbon groups (R') and correspondinglyfrom 3 to 0 of the aforesaid polyether groups (E') can be bonded tosilicon without departing from the scope of this invention. Consistentwith this definition, the monofunctional siloxy units (C) of thepolymers of this invention have the following more specific formula:

H -l-h) wherein R is a monovalent hydrocarbon group, B is the aforesaidpolyether group, and each of g and h has a value of 0 to 3, provided thesum g+h is 3. The preferred monofunctional siloxy units encompassed byFormula 0-1, are those in which g has a value of from 0 to 1 and h has acorresponding value of from 3 to 2.

In view of their monofunctionality, the C units of the polymers of thisinvention cannot extend the polymer network since they arechain-terminating groups. This is in marked contrast to the reactivityof the above-described polyether-substituted diand tri-functionalmonomeric B units encompassed by general Formula B which, in view oftheir polyfunctionality, are chain-extending or polymer-buildingmonomeric units.

The essential polyether group (B) of the diand trifunctional siloxyunits encompassed by Formula B above, and, when present, the polyethergroup (E') of the monofunctional siloxy units (C), are more specificallydefined by the formula, WO(C,,H ,,O) L--, wherein is an organicend-blocked poly(oxyalkylene) chain and -L- is a bivalent organicradical that links the poly(oxyalkylene) chain, (C,,H ,,O) to silicon.When this more specific expression is used in Formula B above in placeof E, the following more detailed definition of the organo-substitutedpolyfunctional siloxy units (B) of the polymers of this invention isprovided:

[WO(C H2 O)d-L] s iO4 (8+0 wherein, as above defined, e has a value offrom 1 to 2, f has a value of from 0 to 1, the sum 2+ is from 1 to 2,and R is a monovalent hydrocarbon radical. Similarly, when the aforesaidformula of the polyether group is used in Formula C-l above in place ofE, the monofunctional siloxy units (C) of the polymers of this inventionare expressed by the following more specific formula:

i [WO(CnHg O)dL] SlO4 (g+h) wherein as above defined, g and h can eachhave a value of from 0 to 3, provided the sum g+h is 3, and R is amonovalent hydrocarbon group. In the poly(oxyalkylene) chain, (C,,H ,,O)of the respective monomeric units B and C of Formulas B3 and 02 above, dis a number having an average value of from about 4 to about 30, and ncan have a value of from 2 to 4, provided at least 75 weight percent ofthe poly(oxyalkylene) chain is constituted of oxyethylene units, (C HO). Usually, the average value of d is from about 5 to about 15, and theaverage value of n is from 2 to 2.25. The other oxyalkylene units withwhich the oxyethylene groups may be in combination are oxypropylene,

and oxybutylene, -(C H O), units. When the oxyethylene units are presentin combination with other oxyalkylene units, the units of differenttypes can be randomly distributed throughout the poly(oxyalkylene) chainor they can be grouped in respective sub-blocks, provided the totalaverage content of --(C H O)- in the chain is at least 75 weightpercent. Preferably, the total average poly(oxyethylene) content of thechain, (C H O) is from about to about weight percent.

The bivalent organic groups represented by --L in the above Formulas B-3and C-2 can be any of a variety of radicals having from 2 to 14 carbonatoms and are usually hydrocarbon groups. Illustrative are such groupsand the like, wherein R", in each instance, is a bivalent branched orstraight chain alkylene radical having the formula, C H m being aninteger having a preferred value of from 2 to 4, of which 3 isparticularly preferred, and R' in each instance is an arylene grouphaving from 6 to 14 carbon atoms, including alkyl-substituted arylenegroups. Typical examples of the linking groups (L) are: ethylene (CH CHtrimethylene (CH CH CH propylene tetramethylene; methylpropylene [--CHCH(CH CH ethylethylene [--CH CH(C H phenylene (C H tolylene and thelike.

As is evident from the above-described classes of bivalent linkingradicals (L), the unsatisfied valences thereof are associated withcarbon and thus form a carbon-to-oxygen bond with the poly(oxyall;ylene)chain and a carbon-to-silicon bond with the silicon atom of therespective siloxy units.

As further indicated by the above Formulas B3 and C-2, thepoly(oxyalkylene) chain, (C H O) is terminated by the organic group,WO-, wherein W is a monovalent organic capping group. Illustrative ofthe organic caps encompassed by W are such groups as:

ROO RNHC(O), and RC(O) wherein R, in each instance, is a monovalenthydrocarbon radical having from 1 to 12 carbon atoms, and is usuallyfree of aliphatic unsaturation. The groups (WO) which end-block thepoly(oxyall ylene) chains are, therefore, corresponding RO, RNHC(O)O-and RC(O)O monovalent organic radicals. In the aforesaid cappying (W)and terminal (WO) groups, R can be any of the following: an alkyl groupincluding linear and branched chain alkyl groups having the formula, CI-I wherein y is an integer of from 1 to 12, such as, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, octyl and dodecylgroups; a cycloaliphatic radical including monocyclic and bicyclicgroups such as, for example, cyclopentyl, cyclohexyl andbicyclo-[2.2.l]heptyl groups; an aromatically unsaturated groupincluding aryl, alkaryl and aralkyl radicals such as, for example,phenyl, naphthyl, xylyl, tolyl, cumenyl, mesityl, t-butylphenyl, benzyl,betaphenylethyl and 2- phenylpropyl groups; alkyland arylsubstitutedcycloaliphatic radicals such as, for example, methylcyclopentyl andphenylcyclohexyl radicals; and the like. It is evident, therefore, thatthe terminal group (WO) of the respective essential polyether groups (E)of the diand trifunctional siloxy units (B) of the polymers of thisinvention, as well as the terminal groups of the polyether groups (E)which may or may not be present in the monofunctional siloxy units (C),can be corresponding alkoxy, aryloxy, aralkoxy, alkaryloxy, cycloalkoxy,acyloxy, aryl-C(O)O, alkyl carbamate and aryl carbamate groups.

The generally preferred R groups are phenyl, lower alkyl radicals, thelower alkyl-substituted aryl groups and the aryl-substituted lower alkylgroups, wherein the term lower alkyl denotes C C alkyl radicals.Therefore, illustrative of the preferred capping groups represented by Wof the above Formulas B-3 and C-2 are: methyl, ethyl, propyl, butyl,phenyl, benzyl, phenylethyl acetyl, benzoyl, methylcarbamyl [CH NHC(O)],ethylcarbamyl [C H NHC(O)L propyland butyl-carbamyl groups,phenylcarbamyl [C H NHC(O)-], tolylcarbamyl [(CH C H NHC(O)],benzylcarbamyl and the like.

It is to be understood that the terminal organic radical (WO) of therespective polyether groups of the polymers of this invention may be thesame throughout the polymer or may differ as between monomeric units.Likewise, the WO-- radical may also be the same or different within anyparticular unit containing more than one polyether group such as thedifunctional siloxy units (B) of the E SiO type (encompassed by FormulaB-l above), or the monofunctional siloxy units (C) of the E R'SiO or E'SiO type (defined with reference to Formula Cl above). For example, thepolymer compositions of this invention can contain polyether groups inwhich the terminal group (WO) is benzyloxy (C H CH O) and otherpolyether groups in which WO- is a hydrocarbylcarbamate group such asmethylcarbamate,

When the polyfunctional siloxy units (B) of the polymers of thisinvention are difunctional, preferably one polyether group is bonded tosilicon and the remaining valence of silicon is bonded to a monovalenthydrocarbon group, designated hereinabove as R. Thus, when in FormulaB3, for example, 9 is 1 and f is also 1, the difunctional units have thepreferred structure:

wherein W, -(C H O) and L are as defined with specific reference toFormula B3. As also described above, monovalent hydrocarbon groups,designated as R, can also be bonded to the silicon atom of themonofunctional siloxy units (C) as defined by general Formula C-l above(that is, when h of Formula C-l has a value of 1, 2 or 3). Themonovalent hydrocarbon groups represented by R and R are free ofaliphatic unsaturation and contain from 1 to 12 carbon atoms, and can beany of the following: an alkyl group including linear and branched chainalkyl groups encompassed by the formula, C H wherein y is an integerfrom 1 to 12; a cycloaliphatic radical including monocyclic and bicyclicgroups; an aromatically unsaturated group including aryl, alkaryl andaralkyl radicals; and other combinations of the aforesaid groups such asalkyland aryl-substituted cycloaliphatic radicals; and the like.

Typical of the aforesaid respective classes of R and R groups are:methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, octyl and decylgroups; cyclopentyl, cyclohexyl and bicyclo[2.2.l]-heptyl groups; phenyland naphthyl groups; xylyl, tolyl, cumenyl, mesityl and t-butylphenylgroups; benzyl, beta phenylethyl, and 2 phenylpropyl groups;methylcyclopentyl and phenylcyclohexyl; and the like.

Of the alkyl groups represented by R and R, the lower alkyl groupshaving from 1 to 4 carbon atoms are preferred of which methyl isespecially suitable. It is to be understood that within any one of themonofunctional hydrocarbylsiloxy units of the polymers of thisinvention, the R groups may be the same or different and that, asbetween monofunctional units, the R groups may also be the same ordifferent. Similarly, as between the preferred difunctional siloxyunits, (E) (R)SiO of the polymers of this invention, the respective Rgroups may be the same or different and may or may not be the same asthe R groups of the monofunctional units. In the most preferred polymersof this invention, the monofunctional siloxy units (C) are of the R SiOtype, the difunctional units are of the (E) (R)SiO type, and essentiallyall of the R and R groups bonded to the silicon atoms are methyl groups.

The novel organosilicone polymers of this invention are depicted by thegeneral expression,

in which the reoccurring monomeric units A are SiO and the reoccurringmonomeric units B and C, are as described above with specific referenceto Formulas B and C1. When these respective definitions of the A, B andC units are included in the above expression, the polymeric compositionsof this invention are expressed as follows:

wherein E and E are polyether groups having the formula, WO-(C,,H ,,O)-L-, in which WO-- is an organic terminal group of the poly(oxyalkylene)chain and L is a bivalent hydrocarbon radical that links the chain tosilicon, as defined above with particular reference to Formulas B-3 andC-2; and, as also previously defined, R and R are monovalent hydrocarbongroups, e is from 1 to 2 and f is from to 1, provided the sum e+f isfrom 1 to 2, and each of g and h can be 0 to 3, provided the sum g+h is3; and the relative proportions of monomeric units A, B and C, expressedon a mole basis, are defined by the relative values of a, b and 0,respectively. The polymers of this invention contain from about 0.4 toabout 2 moles of A per mole of B, and from about 0.2 to about 2 moles ofC per mole of B. Therefore, in the above expressions D and D-l, theratio of a:b is from about 0.421 to about 2:1, and the ratio of 0:12 isfrom about 0.2:1 to about 2:1.

The polymers of this invention have a total polyether content of fromabout 50 to about 85 weight percent and a corresponding total siloxanecontent of from about 50 to about 15 weight percent, the said polyetherand siloxane contents being based on the combined total weight of themonomeric units A, B and C. As used herein, the expression totalpolyether content denotes the sum of the combined total weights of: (1)the polyether groups (E) that are bonded to silicon of thepolyfunctional siloxy units ('B), and (2) the polyether groups (13) whensuch groups are present in the monofunctional triorganosiloxy units (C).Accordingly, the expression total siloxane conten denotes the sum of thecombined total weights of: (1) the SiO units, (a) the polyfunctional Bunits less the total weight of the polyether groups (E), and (3) themonofunctional units less the total weight of the polyether groups (E')which may be present therein.

The organosilicone polymers of this invention can contain thetetrafunctional A units in combination with one or more of the varioustypes of B and C units encompassed by the above Formulas B and C-1,respectively Illustrative of such combinations are the following:

[Sl04 z]=[ -i 2/2]bi[ 'aSiOi/tlxW'aSiOi/fl h D-9 wherein E, E, R and Rhave the aforesaid significance; v, w, x and z are positive numbers, thesum v+w being equal to b and the sum x+z being equal to c; the moleratio of the SiO units to total polyether-substituted polyfunctionalunits to total monofunctional units (that is, the mole ratio of theunits, respectively) is defined by azbzc in which latter ratio thevalues of a, b and c are as aforesaid (that is,

a is from about 0.4 to about 2, b is 1, and c is from about 0.2 to about2); and the total polyether content is main- 10 tained within theaforesaid range of from about 50 to about Weight percent, based on thecombined total weight of the monomeric units.

The polymers of this invention are generally useful as surfactants andinclude compositions which find particular application in themanufacture of polyester urethane foam, including flame-retarded foam.Of the novel polymeric surfactants described herein, a generallypreferred class, particularly for use in the formation of flexiblepolyester urethane foam, are the polymers represented by the followingexpression:

wherein R and R are preferably lower alkyl radicals having 1 to 4 carbonatoms, the link between the organicterminated poly(oxyalkylene) chainand silicon is provided by the bivalent alkylene radical, C H (mpreferably being from 2 to 4); from 75 to about 10-0 weight percent ofthe poly(oxyalkylene) chain is attributable to oxyethylene units andfrom 25 to 0 weight percent is constituted of oxypropylene units; 0! hasa preferred average value of from about 5 to about 15; and the moleratio of the tetrato dito mono-functional monomeric units is asaforesaid (that is, azbzc is about 0.4-2: 1:0.2-2).

From the standpoint of providing greater operating latitude (that is,less dependency of foam quality, for example, on variables such as theconcentration of surfactant in the foam-producing reaction mixture), itis generally preferred that the polymer contain from about 0.6 to about1.8 moles of SiO units (A) per mole of polyfunctional siloxy units (B),from about 0.8 to about 1.8 moles of monofunctional siloxy units (C) permole of polyfunctional siloxy units (B), and less than 3, and mostpreferably not more than 2.8, total moles of A+C units per mole of Bunits. Thus, in the preferred azbzc ratio, a is from about 0.6 to about1.8, b is 1, and c is from about 0.8 to about 1.8, and most preferably,a-l-c:b is from 1.4:1 to 2.821.

From the standpoint of having a superior over all combination ofproperties for the stabilization of flexible polyester foam, the mostpreferred polymers of this invention are as follows:

wherein d has an average value of from about 5 to about 15; m has avalue of from 2 to 4: a:b:c has the aforesaid preferred value of0.6l.8:l:0.8-1.8, provided a+c:b is 1.4-2.8:1; and R is phenyl, loweralkyl, lowe alkaryl or aryl-substituted lower alkyl groups. Particularlyelfective for the stabilization of flame-retarded flexible polyesterurethane foams, are polymers in which at least a major proportion of thepoly(oxyalkylene) chains are terminated by RO- groups where the organiccap (R) is benzyl.

In the preparation of the organosilicone polymers of this invention,silicon-containing reactants, designated herein as reactants A, B and C,are employed in which silicon is bonded directly to hydrolyzable groupsthe number of which corresponds to the number of oxygen atoms bonded tosilicon of the respective monomeric units A, B and C. The hydrolyzablegroups can be halogen, radicals bonded to silicon through an oxygenatom, and any combination thereof. Illustrative of suitable reactants(A') from which the tetrafunctional monomeric units (A) are derived arethose encompassed by the general formula:

wherein X is halogen (usually chlorine or bromine), Y is a hydrocarbonradical such as alkyl, aryl and aralkyl, and the like, and p, q and rcan each have a value of zero to 4, provided the sum p+q+r is four.Typical examples of this reactant are silicon tetrachloride, lower alkylorthosilicates having the formula, Si(OY') wherein q is 4, and thepartial lower alkyl esters of silicon tetrachloride, (Cl) Si(OCOY)wherein each of p and r has a value of from 1 to 3, provided p-l-r is 4,and Y in each instance is an alkyl group having from 1 to 4 carbonatoms. Tetraethoxysilane (also known as tetraethyl orthosilicate orsimply as ethyl orthosilicate) is especially suitable as the A reactant.

Reactant B which is the ultimate source of the polyether-substitutedpolyfunctional monomeric B units contains from 2 to 3 hydrolyzablegroups bonded to silicon depending upon whether it is desired to providedifunctional or trifunctional units in the polymer. Suitable as the Breactants are compounds encompassed by the general formula:

wherein R corresponds to the monovalent hydrocarbon group (R) of thepolyfunctional B units encompassed by general Formula B above; E iseither hydrogen or the polyether group (E) of general Formula B above,having the more specific structure, WO(C H O) L, wherein the bivalentlinking group (L-) is preferably an alkylene group, C H as defined abovewith reference to Formula B3; e and also have the same significance asin the monomeric polyfunctional B units (that is, e is from 1 to 2, f isfrom to 1, and the sum e-l-f is 1 to 2); X and Y are as above-definedwith respect to reactant A, and each of s, t and u can be 0 to 3,provided the sum s-l-t-l-u is from 2 to 3, and the sum e+f+s+l+u is 4.

Illustrative of the various types of reactants encompassed by Formula Bare the following:

wherein R and the preferred organic capped polyether group, WO(C H O) CH are as above-defined with specific reference to Formula B3 ofpolyfunctional monomeric units B, X is halogen (usually chlorine) and Yis usually a lower alkyl group (Y') such as methyl or ethyl. In thepreparation of organosilicone polymers of this invention in which acombination of different polyfunctional siloxy units B are present, suchas the and E-SiO units, more than one B reactant is required. Forexample, in preparing the polymers illustrated above as D6 and D7, therespective diand tri-functional siloxy units are obtained by employing acombination of corresponding B reactants such as the aforesaid reactantsB'l and B'7. Alternatively, such polymers are provided by employing acombination of hydrosilanes such as reactants B-2 and B'8, as the sourceof the siloxane portions of the respective B units, and thesilicon-bonded hydrogen is subsequently replaced by the polyether groups(B), as described hereinbelow. It is to be understood that a combinationof polyether-substituted and hydrogen-substituted reactants such as B 1and B'8 can also be employed without departing from the scope of thisinvention.

Reactant C which is the ultimate source of the monofunctionaltriorganosiloxy units (C) of the polymers of this invention, containsone hydrolyzable group and is represented by the following generalformula:

E'Q-Si-Z (0') wherein R corresponds to the monovalent hydrocarbon group(R') of the monofunctional C units encompassed by Formula C-l above; Eis either hydrogen or the polyether group (E') of Formula C-l above,having the more specific structure, WO-(C H ,,O) L, wherein the bivalentlinking group (--L) is preferably an alkylene group (-C H as abovedefined with specific reference to Formula C2; g and h also have thesame significance as in the monofunctional monomeric C units (that is,each of g and h can be from 0 to 3, provided their sum is 3); Z can beany of the aforesaid hydrolyzable groups, designated as X, OY andOC(O)Y, and can additionally be a hydroxyl group or, when g is zero, Zcan also be an -OSiR group in which event the C reactant is adisiloxane.

Illustrative of the various types of reactants encompassed by Formula Care the following:

wherein R and the preferred organic capped polyether group, WO--( C H O)C H are as defined with specific reference to Formula C-2 above of themonofunctional C units; X is halogen (usually chlorine) and Y is usuallya lower alkyl group (Y') such as methyl or ethyl. In preparingorganosilicone polymers of this invention in which a combination ofdifferent monofunctional siloxy units are present, such as the R' SiOand (R') (E)SiO units, more than one C reactant is required. Forexample, in preparing the polymers illustrated above as D-7 and D-8, therespective monofunctional units are obtained by employing a combinationof corresponding C reactants such as the aforesaid reactants C'l andC'S, or the aforesaid reactants C-1 and C'7. When employing ahydrosilane such as reactant C-7, the silicon-bonded hydrogen issubsequently replaced by the polyether group (E'), as describedhereinbelow.

The organosilicone polymers of this invention are produced by theprocess which comprises cohydrolyzing the above-described reactants A, Band C and cocondensing the hydrolyzate, thereby providing either thepolymer composition of the invention as the direct product of thecohydrolysis-cocondensation reaction, or an intermediate silcxanepolymer product containing siliconbonded hydrogen which is reactedfurther to substitute silanic hydrogen with polyether groups. ReactantsA, B and C are employed in respective amounts selected to provide thecorresponding monomeric A, B and C units in the relative molarproportions defined above as the azbzc ratio in which ratio the valuesof a and c are from about 0.4 to about 2 and from about 0.2 to about 2,respectively, expressed on the normalized basis of b =1. Accordingly, inproducing the polymers of this invention, from about 0.4 to about 2moles of A are employed per mole of B and from about 0.2 to about 2moles of C are employed per mole of B'. Water is preferably used in anamount at least suflicient to satisfy the stoichiometry of thecohydrolysis reaction. Usually, water is used in a 10 to 200 percentmolar excess of the stoichiometric requirements, although more than a200 percent molar excess can be employed without departing from thescope of this embodiment of the present invention.

The cohydrolysis-cocondensation reaction for producing the novelpolymers described herein is illustrated by the following equation (1)wherein for convenience, tetraethoxysilane is shown as reactant A, andchlorine is shown as the hydrolyzable groups of reactants B and shown asthe hydrolyzable groups of reactants B and C:

Equation 1 wherein, as above-defined, E' is either hydrogen or apolyether group (B); E is either hydrogen or a polyether group (B); Rand R are monovalent hydrocarbon groups; 2 is from 1 to 2 and f is fromto 1, provided e+f is from 1 to 2; s is from 2 to 3, provided e+f+s is4; each of g and It can be 0 to 3, provided g-l-h is 3; a, b and c whichrepresent the number of moles of the indicated A, B and C reactants, canbe any positive numbers provided the ratio thereof, that is, a':b':c',when expressed on the normalized basis of b'=l, is about 0.42:1:0.2-2,thereby providing polymers in which the respective monomeric units A, Band C are present in corresponding molar proportions, the a:b:c ratioalso being about 0.42:1:0.2-1. Provided the ratio of the number of molesof reactants employed is as specified, the actual number of molesemployed (and thus the quantity of polymer produced) can be any multipleof the a':b:c ratio, depending upon the scale on which it is desired tocarry out the reaction.

When the B reactant employed in the cohydrolysiscocondensation reactionof equation (1) is a hydrosilane (such as, for example, reactants B-2,B'-6 and B'-8 above), the product thereof is reacted further with amonoolefinic poly(oxyalkylene) ether having the formula WO(C,,H ,,O) C HIn the ether reactant, the moiety, WO-(C H O) is as above-defined withrespect to the corresponding organic terminated poly(oxyalkylene) chainof the polyether substituted polyfunctional siloxy units (B), and C H isa monovalent olefinic group wherein m has the same significance as inthe bivalent alkylene group (C H of the polyether substituents (E) ofmonomeric units B (that is, m has a value of from 2 to 14, and isusually from 2 to 4). This embodiment of the method for producing thenovel polymers of the present invention is illustrated by the reactionsof the following equations (2) and (3) wherein tetraethoxysilane and atrihydrocarbyl monochlorosilane typically illustrate the A and Creactants, respectively, the B reactant is shown as ahydrocarbyl-substituted di- 14 chlorohydrosilane, and, for the purposeof illustration, the A, B and C reactants are used in equimolarproportions:

Equation 2 Since the reaction of equation (2) is illustrated on thebasis of equimolar amounts of reactants A, B and C, the mole ratio ofa:b:c in equations (2) and (3) is, of course, 1:1:1. When the C reactantcontains silanic hydrogen, the product of thecohydrolysis-cocondensation reaction is reacted in a similar manner withthe aforesaid monoolefinic ether reactant to provide monomeric C unitscontaining a polyether substituent (E'). Further, when reactant B (or C)contains more than one siliconbonded hydrogen atom as in reactant B-6above, for example, the intermediate product of the reaction of equation(2), is reacted with a corresponding number of moles of the monoolefinicpolyether reactant.

In accordance with another embodiment of the process for preparing thenovel organosilicone polymers of this invention, the B reactant is onein which E of the above Formula B is a polyether group (B) rather thanhydrogen, and the polymers are produced as the direct product of thecohydrolysis-cocondensation reaction. This embodiment is illustrated bythe reaction of the following equation (4) wherein tetraethoxysilanetypically illustrates the A reactant, B is shown as a mono(polyether)-substituted hydrocarbyldichlorosilane, C is illustrated as atrihydrocarbylchlorosilane, and reactants A, B and C are employed inequimolar amounts:

Equation 4 wherein R, R, W0, n, d and m are as previously defined hereinand the mole ratio (a:b:c) of the repective monomeric units is 1:1:1. Inproviding polymers of this invention in which the monomeric B units aretrifunctional (that is, E-SiO the reaction of equation (4) is carriedout employing a mono(polyether)-substituted silane containing threehydrolyzable groups as the B reactant such as, for example, thetrichlorosilane having the formula, WO(C,,H ,,O) C H -SiCl Further, inproducing polymers of this invention containing one or more of thepolyether-substituted monofunctional C units of the yp )2 1/21 ')2( i 2the cohydrolysis-cocondensation reaction of equation (4) is efl ectedusing the respective mono-, dior tri-(polyether) substitutedmonochlorosilanes encompassed by Formula C in place of, or in additionto, the R' SiCl reactant shown in equation (4).

Reactants B encompassed by Formula B above in which one or two polyethergroups (B) are bonded to silicon, and reactants C encompassed by FormulaC containing from one to three polyether group (E), are prepared byreacting the aforesaid monoolefinic poly(oxy- 15 alkylene) ethers, WO(CH O) C H with hydrosilanes in which the number of silicon-bondedhydrogen atoms corresponds to the number of polyether groups desired inthe monomeric B or C units. For example, the B reactant shown inequation (4) above, is prepared in accordance with the followingequation (5), and reactants C of the (E)(R') SiCl and (E') (R)SiCl type,are prepared as illustrated by equations (6) and (7) below.

wherein R, R, WO, n, d and m have the previously defined significance,and the monolefinic group, C H is preferably vinyl, ally or methallyl,the allyl group being especially suitable. The monoolefinic polyetherreactants used in the reactions of equations (3) and (5)(7) above, canbe prepared by starting alkylene oxide polymerization with amonoolefinic alcohol such as allyl alcohol to provide HO-(C,,H O) C H-(wherein n and d are as previously defined herein and m has a value ofat least 3), followed by capping of the terminal hydroxyl group with theaforesaid organic radical, W-, such as methyl, phenyl, benzyl, acetyl,methylcarbamyl and like capping groups. Further details concerning themethod of preparation of such polyether reactants are disclosed inpending US. application Ser. No. 109,587, filed Jan. 25, 1971, of E. L.Morehouse, now abandoned. Alternatively, the polyether reactants can beprepared by starting the alkylene oxide polymerization with an alkanolsuch as methanol, an aralkyl alcohol such as benzyl alcohol, a phenoland the like, followed by capping of the terminal hydroxyl group of thereaction product with the monoolefinic group such as vinyl, allyl,methallyl and the like. Of these various polyether reactants, allylalcohol-started poly(oxyalky1ene) ethers are especially suitable.

The addition of the silanic hydrogen of the respective silane reactantsof equations (5)-(7), as well as the addition of the silicon-bondedhydrogen of the intermediate polymer product shown by the reaction ofequation (3), to the monolefinic group, H

of the polyether reactant, is platinum-catalyzed. Usually, platinum isused in the form of chloroplatinic acid in a catalytic amount such asfrom 5 to 150, preferably from 10 to 50, parts per million parts byweight of the siliconcontaining and polyether reactants. Suitablereaction temperatures range from about room temperature (25 C.) to about150 C. If desired, the addition reaction may be conducted in thepresence of liquid aromatic hydrocarbons such as toluene and xylene,although other non reactive solvents can be used.

When the organic radical (W-) of the terminal group (WO-) of thepoly(oxyalkylene) chain of the dior trifunctional monomeric units (B) isa monovalent hydrocarbon group (that is, the above-defined R-group) suchas methyl, phenyl and benzyl groups, the novel polym r dSGIibd hereinare preferably prepared in accordance with the method illustrated by thereaction of equation (4) above, in which the B reactant already containsthe polyether group (B) and the polymer is the direct product of thecohydrolysis-cocondensation reaction. Likewise, polymers in which themonofunctional siloxy units (C) contain polyether groups (E') capped bya monovalent hydrocarbon radical (R), are also preferably prepared asthe direct product of the cohydrolysis-cocondensation reaction. When theorganic cap (W-) of the polyether group of the B units (or C units) isan acyl (RCO) or carbamyl (RNHCO) group, it is usually preferred toprepare the polymers of this invention in accordance with the reactionsof equations (2) and (3) whereby, as shown, the polyether groups (E and,when present, E) are introduced in a step subsequent to thecohydrolysis-cocondensation reaction.

The above-described cohydrolysis-cocondensation reactions for producingthe organosilicone polymers of this invention can be carried out attemperatures from about 25 C. to about 150 C., in the presence orabsence of a solvent or diluent. The presence of solvents may aid byincreasing compatibility between reactants, effecting distribution, andthereby avoiding gel formation and controlling reaction rates. Usefulsolvents are aromatic hydrocarbons (such as, for example, toluene andxylene), mixtures of aromatic hydrocarbons, low molecular weightalcohols (such as, for example, isopropanol), ethers including lowmolecular weight polyethers in which hydroxyl groups initiallyterminating the chains have been capped with an organic group (such as,for example, methyl) and other solvents which are non reactive withsilicon-bonded functional groups (such as Si-H, Si--Cl and Si--OY) ofthe A, B and C reactants.

The by-products of the cohydrolysis-cocondensation reaction depend, ofcourse, on the nature of the hydrolyzable groups of the A, B and Creactants, and are readily removed from the polymeric product, usuallyby fractional distillation. For example, the ethanol and hydrochloricacid formed as by-products of the illustrative reactions of equations(1), (2) and (4) above, are readily removed, together with excess water,as a azeotrope. As desired, any organic solvent used in the polymerpreparation is also removed by conventional separation techniques toobtain a substantially percent active polymer composition. After removalof by-prodnets and water a substantially neutral product of thecohydrolysis-cocondensation reaction is provided. Althoughneutralization is usually not necessary, sodium bicarbonate may be addedand the polymer product filtered to remove platinum residues introducedduring the platinum-catalyzed preparation of the polyether-substituted Band C reactants, as illustrated by equations (5)-(7) above, or duringthe platinum-catalyzed reaction of the intermediate polymeric productcontaining silanic hydrogen with the above-described monoolefinicpolyether reactants, as illustrated by equation (3) above.

In addition to the monomeric A, B and C units, the polymers of thisinvention may contain residual silanols and residual hydrolyzable groupsremaining from the reactants employed in the preparation thereof, Inaddition, a small percentage (on the average, usually about 10 molepercent or less) of the total polyether groups (E and, when present, E)may be residual, uncapped hydroxyl-terminated groups [that is, HO-(C,,H,,O) C H introduced with the monoolefinic poly(oxyalkylene) etherreactants employed in the reactant of equation (3) above, or in thepreparation of the B (or C) reactants as illustrated by the aboveequations (5)-(7). In the use of the polymers of this invention asstabilizers of polyester foam, the total weight of the aforesaidresidual groups should be no higher than about 10 weight percent, and ispreferably less than 6 weight percent, based on the total Weight of thepolymer.

The content of such residual groups is substantially reduced andminimized by treatment of the polymeric products with an organicisocyanate in the presence of an amine catalyst such as those describedhereinbelow as suitable for the urethane-forming reaction (for example,triethylamine and N-ethylmorpholine), or a metal catalyst such asorgano-tin compounds (for example, stannous octoate, dibutyltin laurate,and the like). Usually, the organic isocyanate employed in thistreatment is an alkyl, aryl or arakyl mono-isocyanate, such as methyl,ethyl, phenyl, benzyl isocyanates, and the like. The treatment of thepolymer product in this manner may be carried out in the presence orabsence of a solvent or diluent. Aromatic hydrocarbons such as Xyleneand toluene are suitable as the solvent medium.

The polymer compositions of this invention are liquids and havemolecular weights which vary over a relatively wide range. Generally,the average molecular weights of the polymers of this invention rangefrom about 1000 to about 20,000 (as measured by Gel PermeationChromatography using a calibration curve based on dimethylsiloxanefluids).

The organosilicone polymers of this invention are mixtures of polymerspecies which difier in molecular weight, polyether and siloxanecontents, and relative molar proportions of the monomeric units. It isto be understood, therefore, that as expressed herein, the values ofthese parameters are average values.

The organosilicone polymers of this invention are effective asstabilizers of flexible polyester urethane foams and can, therefore, beused as such without the need for combination with an anionic orcationic organic surfactant, or other type of organic additive. Thepolymers can be employed as a 100 percent active stream, or they can beemployed in dilute form as a solution in polar solvents (e.g., glycols)or non polar organic solvents such as normally liquid aliphatic and andaromatic unsubstituted and halogen-substituted hydrocarbons (e.g.,heptane, xylene, toluene, chlorobenzenes and the like). In addition tothe polymers, the other essential types of components and reactantsemployed in the production of flexible polyester urethane foam inaccordance with the process of this invention are polyester polyols,organic polyisocyanates, amine catalyst and blowing agent. Whenproducing self-extinguishing foams, the foam-producing reaction mixturesalso contains a flame retardant. The organosilicone polymers of thisinvention are usually present in the final foam-producing reactionmixture in amounts of from about 0.15 to about 4.0 parts by weight per100 parts by weight of the polyester polyol reactant.

It is often the preferred practice of foam manufacturers to premix thefoam stabilizer, amine catalyst and water (which is the usual source ofat least part of the blowing action), and to feed the aqueous premixtureto the foamproducing reaction mixture as a single stream. The meremixing of the organosilicone polymers of this invention with thecatalyst and water, however, forms a heterogeneous mitxure whichdetracts from the processing advantage of adding these components as acombined stream rather than as individual streams. The problem of premixincompatibility is overcome in accordance with the present invention byproviding homogeneous aqueous premixtures comprising the organosiliconepolymer, amine catalyst, an organic acidic component and, as anadditional ingredient, either a water soluble organic surfactant or awater soluble glycol, or both of the latter two types of components.Although these various organic additives can be introduced directly tothe aqueous premixture of foam stabilizer and catalyst, the formation ofclear, homogeneous aqueous solutions is facilitated by blending theadditives with the foam stabilizer (that is, the organosilicone polymersof this invention) and combining the resulting blend with water and theamine catalyst system. In accordance with another embodiment of thisinvention, therefore, solution compositions are provided comprising theorganosilicone polymers of this invention,

an organic surfactant and glycol. The organosilicone polymer is presentin the solution compositions in an amount of from about 10 to aboutparts by weight per 100 parts by weight of the solution.

The aforesaid organic acidic component comprises the saturated andunsaturated aliphatic and cycloaliphatic carboxylic acids containingfrom 15 to 20 carbon atoms. Illustrative of suitable acidic componentsare the fatty acids such as, for example, palmitic, stearic,palmitoleic, oleic, linoleic, linolenic and ricinoleic acids; resinacids of the abietic and pimaric type; and any combination of theaforesaid acids as well as industrial by-products andnaturally-occurring materials comprising such acids. An especiallysuitable acidic component of the solution compositions and aqueouspremixtures of this invention is tall oil which is a by-product ofsulfate digestion of wood pulp and is composed largely of fatty acids(oleic, linoleic, linolenic and palmitic acids) and resin acids, and aminor amount of neutral material such as fatty acid esters.

The above-described organic acidic component is present in the solutioncompositions of this invention in an amount of from about 5 to aboutparts by weight per parts by weight of organosilicone polymer present inthe solution.

The water-soluble organic surfactant which can be a component of thesolution compositions of this invention may be of the nonionic, anionic,cationic or 'amphoteric types, including combinations thereof.Preferably, the organic surfactant is a non ionic surfactant such as:the p0ly(0xy-alkylene) ethers of the higher alcohols having from 10 to18 carbon atoms including mixtures thereof; polyoxyalkylene ethers ofalkyl-substituted phenols in which the alkyl group can have from 6 to 15carbon atoms; and corresponding polythio-alkylene adducts of theaforesaid higher alcohols and phenols. The length of the ether chain issuch that appropriate hydrophilic character is provided to balance thehydrophobic portion derived from the alcohol or phenol and render thecompound soluble in water. The chain may contain oxyethylene unitseither as essentially the sole type of unit or oxyethylene incombination with a minor amount of oxypropylene. It is preferred thatthe hydrophilic portion of the non ionic surfactants be composedessentially of oxyethylene monomeric units. Usually the average numberof such OC H units ranges from about 4 to about 20, although upwards of40 such units can also be present.

Typical examples of nonionic surfactants which can be used as componentsof the solution compositions of this invention are the adducts producedby reaction of k moles of ethylene oxide (wherein k has a value of fromabout 4 to about 40, inclusive of whole and fractional numbers) per moleof any of the following hydrophobes including mixtures thereof:n-undecyl alcohol, myristyl alcohol, lauryl alcohol, trimethyl nonanol,tridecyl alco hol, pentadecyl alcohol, cetyl alcohol, oleyl alcohol,stearyl alcohol, nonylphenol, dodecylphenol, tetradecylphenol, and thelike.

Other illustrative water soluble organic surfactants which can bepresent as a component of the solution compositions of this inventionare: sodium, potassium, ammonium and quaternary ammonium salts ofsulfonic acids wherein the hydrocarbyl portion can be alkyl or alkarylgroups containing from 10 to 20 carbon atoms. Examples of such organicsurfactants are: sodium tetradecyl sulfonate and sodium dodecylbenzenesulfonate; sodium and potassium salts of sulfonated petroleum fractionssuch as mineral oil; diethylamine salts of sulfonated C -C alkylatedaromatic hydrocarbons; taurine compounds having at least one long chainhydrocarbyl group bonded to nitrogen; and the like.

The solution compositions of this invention may also contain, as a thirdtype of organic component, a glycol of from 2 to about 10 carbon atoms,or low molecular weight Carbowax polyethylene glycols. Especiallysuitable is hexylene glycol (2-methyl-2,4-pentanediol).

When both the organic surfactant and glycol components are present inthe solution compositions of this invention, the combined concentrationthereof ranges from about 5 to about 90 parts by weight per 100 parts byweight of the organosilicone polymer contained therein. When only one ofthese components is present, the concentration thereof is also withinthis latter range.

When the aforesaid solution compositions of the organosilicone polymersof this invention are combined with water and amine catalyst such as thecatalysts described hereinbelow, clear, homogeneous aqueous solutionsare obtained which can be added directly to the foam-producing reactionmixture. From the standpoint of retaining these desirablecharacteristics of clarity and homogeneity under otherwise adverseambient temperatures which may be encountered upon standing, storage orshipment prior to use in the foam-producing reaction, the preferredaqueous premixtures are those containing both the organic surfactant (ofwhich non ionics are preferred) and the glycol, in addition to theorganic acidic component. It is to be understood that the aforesaidsolution compositions of the organosilicone polymers of this inventionare also useful when added directly to the final foam-producing reactionmixture rather than being premixed with water and amine catalyst.

The solution compositions of the foam stabilizer as well as the aqueouspremixtures of this invention, can contain minor amounts of otheringredients without departing from the scope of this invention. Suchcomponents include inhibitors such as for example, d-tartaric acid,tertiary-butyl pyrocatehol and di-tert-butyl-p-cresol (Ionol), whichreduce any tendency of the foamed product to oxidative or hydrolyticinstability. Further, when the foam stabilizers of this invention and/orthe amine catalyst are employed as respective solutions, water solublecarrier solvents and components thereof are, of course, introduced intothe aqueous premixtures without, however, any deleterious effect on theeffectiveness or homogeneity of the aqueous solution premixtures.

The relative proportions of the organosilicone foam stabilizer of thisinvention, the amine catalyst and water in any particular solution arelargely dependent upon and determined by the relative proportions ofsuch ingredients which are desired in a particular foam-producingreaction mixture. Accordingly, in the preparation of a particularaqueous premixture of this invention, the relative proportions of thefoam stabilizer, amine catalyst and water are adjusted and the aqueouspremixture is added to the final foam-producing formulation in an amountsufiicient to satisfy the respective functions of such components and toprovide a foamed product of desired quality.

The polyester polyols employed in producing flexible foams in accordancewith the process of this invention are the reaction products ofpolyfunctional organic carboxylic acids and polyhydric alcohols. Thepolyester polyols contain at least two hydroxyl groups per molecule (asalcoholic OH or as OH in COOH groups). The functionality of these acidsis preferably provided by carboxy groups (COOH) or by both carboxygroups and alcoholic hydroxyl groups. The polyesters can have hydroxlynumbers from 30 to 150, and preferably have hydroxyl numbers from 45 to65. These hydroxyl numbers are readily determined according to theprocedure described by Mitchel et al., organic analysis, Volume I(Interscience, New York 1953).

Typical of the polyfunctional organic carboxylic acids that can beemployed in producing polyester polyols useful in this invention are:dicarboxylic aliphatic acids such as succinic, adipic, sebacic, azelaic,glutaric, pimelic, malonic and suberic acids; and dicarboxylic aromaticacids such as phthalic acid, terephthalic acid, isophthalic acid and thelike. Other polycarboxylic acids that can Cir be employed are the dimeracids such as the dimer of linoleic acid. Hydroxyl-containingmonocarboxylic acids (such as ricinoleic acid) can also be used.Alternatively, the anhydrides of any of these various acids can beemployed in producing the polyester polyols.

The polyhydric alcohols (organic polyols) that can be employed inproducing the polyester polyol starting material used in the process ofthis invention include the monomeric polyhydric alcohols such as, forexample, glycerol; 1,2,6-hexanetriol; ethylene glycol; diethyleneglycol; trimethylol propane; trimethyolethane; pentaerythritol;propylene glycol; l,2-, 1,3- and 1,4-butylene glycols; 1,5-pentanediol;sorbitol; and the like, including mixtures thereof.

Other polyhydric alcohols that can be employed in producing thepolyester polyols useful in this invention are the polymeric polyhydricalcohols which include the linear and branched chain polyethers having aplurality of acyclic ether oxygens and at least two alcoholic hydroxylradicals. Illustrative of such polyether polyols are thepoly(oxyalkylene) polyols containing one or more chains of connectedoxyalkylene radicals which are prepared by the reaction of one or morealkylene oxides with acyclic and alicyclic polyols. Examples of thepoly(oxyalkylene) polyols include the poly(oxyethylene) glycols preparedby the addition of ethylene oxide to water, ethylene glycol ordiethylene glycol; poly(oxypropylene) glycols prepared by the additionof propylene oxide to water, propylene glycol or dipropylene glycol;mixed oxyethylene-oxypropylene polyglycols prepared in a similar mannerutilizing a mixture of ethylene oxide and propylene oxide or asequential addition of ethylene oxide and propylene oxide; and the poly-(oxybutylene) glycols and copolymers such as poly-(oxyethylene-oxybutylene) glycols and poly(oxypropylene-oxybutylene)glycols. Included in the term poly- (oxybutylene) glycols are polymersof 1,2-butyleneoxide and 2,3butyleneoxide.

Illustrative of further polyester polyol reactants that are useful inproducing flexible polyester urethane foam in accordance with theprocess of this invention are the reaction products of any of theaforesaid polycarboxylic acids and the polyhydric alcohols prepared bythe reaction of one or more alkylene oxides such as ethylene oxide,propylene oxide, butylene oxide and mixtures thereof, with any of thefollowing: glycerol; trimethylolpropane; 1,2,6-hexanetriol;pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl,butyl and 2- ethylhexyl arabinoside, xyloside, fructoside, glucoside,and rhammoside; sucrose; mononuclear polyhydroxybenzenes such asresorcinol, pyrogallol, phloroglucinol, hydroquinone,4,6-di-tertiarybutylcatechol, and catechol; polynuclear hydroxybenzenes(polynuclear designating at least two benzene nuclei) such as the di-,triand tetraphenylol compounds in which two to four hydroxybenzenegroups are attached either directly by means of single bonds or throughan aliphatic hydrocarbon radical containing one to twelve carbon atoms,such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and the various diphenols anddiphenol methanes disclosed in United States Pat. Nos. 2,506,486 and2,744,882, respectively. Another type of polyester polyol reactant isthat produced by reaction of a polycarboxylic acid and the polyetheradducts formed by reaction of ethylene oxide, propylene oxide orbutylene oxide with phenol-formaldehyde condensation products such asthe novolaks.

The organic polyisocyanates that are useful in producing flexiblepolyester urethane foam in accordance with the process of this inventionare organic compounds that contain at least two isocyanato groups. Suchcompounds are well known in the art of producing polyurethane foams, andare conveniently represented by the general formula:

wherein i is an integer of two or more and Q is an organic radicalhaving the valence of i. Q can be a substituted or unsubstitutedhydrocarbon group (e.g., alkylene, cycloalykylene, arylene, alkarylene,aralkylene and the like). Q can also be a group having the formulaQ'-Z-Q' wherein Q is an alkylene or arylene group and Z is a divalentmoiety such as -O-, -O-Q'-O-, -C(O-) -S-, -S-Q'-S-, or -SO Illustrativeof suitable organic polyisocyanate reactants are the following includingmixtures thereof:

1,2-diisocyanato-ethane; 1,3-diisocyanato-propane;1,4-diisocyanato-butane; 1,S-diisocyanato-pentane;1,6-diisocyanato-hexane; 1,5-diisocyanato-2,2-dimethyl-pentane; 1,7diisocyanato-heptane; 1,5 diisocyanato-2,2,4-trimethyl-pentane; 18-diisocyanato-octane;

1,9 diisocyanato-nonane;

1,10-diisocyanato-decane;

1,1 l-diisocyanato-undecane;

1,l2-diisocyanato-dodecane; 1,6-diisocyanato-3-methoxy-hexane;1,6-diisocyanato-3-butoxy-hexane; bis(3-isocyanato-propyl) ether;

the bis(3-isocyanato-propyl)ether of 1,4-butylene glycol; (OCNCH CH CHOCHQ O;

bis(2-isocyanatoethyl) carbonate; 1-methyl-2,4-diisocyanato-cyclohexane;l,8-diisocyanato-p-menthane;

bis-5,6- (2-isocyanatoethyl) bicyclo [2.2.1 -hept-2-ene;bis(3-isocyanato-propyl)sulfide;

bis isocyanato-hexyl sulfide;

1,4-phenylene-diisocyanate;

2,4-tolylene-diisocyanate;

2,6-tolylene-diisocyanate;

crude tolylene diisocyanates;

xylyene diisocyanates; 4-chloro-l,3-phenylene-diisocyanate;4-bromo-1,3-phenylene-diisocyanate;

4-nitro(l,3 or 1,5)-phenylene-diisocyanate;4-ethoxy-l,3-phenylene-diisocyanate;

benzidine diisocyanate;

toluidine diisocyanate;

dianisidine diisocyanate;

2,4'- or 4,4'-diisocyanato-diphenyl ether;diphenylmethane-4,4'-diisocyanate; 4,4-diisocyanatodibenzyl;isopropyl-benzene-alpha-4-diisocyanate; 1,5-diisocyanato-naphthalene;1,8-diisocyanato-naphthalene;

9, l-diisocyanato-anthracene; triphenyl-methane-4,4',4"-triisocyanate;

2,4,6-toluene triisocyanate;

and many other organic polyisocyanates that are known in the art such asthose disclosed in an article by Siefkeu, Ann., 565, 75 (1949). Ingeneral, the aromatically unsaturated polyisocyanates are preferred.

Further included among the isocyanates useful in the process of thisinvention are dimers and trimers of isocyanates and diisocyanates andpolymeric diisocyanates such as those having the general formula:

[Q(NCO)1]3 in which i and j are integers of two or more, and/or (asadditional components in the reaction mixtures) compounds of the generalformula:

L (NCO) 1 in which i is one or more and L is a monofunctional orpolyfunctional atom or radical. Examples of this type includeethylphosphonic diisocyanate, C H P(O)(NCO) phenylphosphonicdiisocyanate, C H P(O) (NCO) compounds containing an ESl-NCO group,isocyanates derived from sulfonamides (QSO NCO), cyanic acid, thiocyanicacid, and compounds containing a metal-NCO radical such as tributyltinisocyanate.

Also included as useful in the preparation of the flexible polyesterurethane foams in accordance with the process of this invention are thepolyisocyanates of the anilineformaldehyde polyaromatic type which areproduced by phosgenation of the polyamine obtained by acid-catalyzedcondensation of aniline with formaldehyde. Poly(phenylmethylene)polyisocyanates of this type are available commercially under such tradenames as PAPI, AFPI, Mondur MR, Isonate 390 P, NCO-120 and NCO-20. Theseproducts are low viscosity (50500 centipoises at 25 C.) liquids havingaverage isocyanato functionalties in the range of about 2.25 to about3.2 or higher, depending upon the specific aniline-to-formaldehyde molarratio used in the polyamine preparation.

Other useful polyisocyanates are combinations of diisocyanates withpolymeric isocyanates containing more than two isocyanato groups permolecule. Illustrative of such combinations are: a mixture of2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and the aforesaidpoly- (phenylmethylene) polyisocyanates; and mixtures of isomerictolylene diisocyanates with polymeric tolylene diisocyanates obtained asresidues from the manufacture of the diisocyanates.

The polyisocyanate reactant of the foam-producing reaction mixture isgenerally employed in an amount that provides from about to about 150percent, usually from about to about percent, of the stoichiometricamount of the isocyanato groups required to react with all of thehydroxyl groups of the polyester polyol reactant and any water presentas a blowing agent. That is, the total -NCO equivalent to total activehydrogen equivalent is generally within the range of about 0.8 to about1.50, usually about 0.9 to about 1.2, equivalent of -NCO per equivalentof active hydrogen.

The reaction mixtures employed to produce flexible polyester urethanefoam in accordance with the teachings of the present invention alsocontain a catalyst for accelerating the isocyanate-reactive hydrogenreaction. This component usually comprises a tertiary amine and istypically illustrated by the following: N-methylmorpholine;N-ethylmorpholine; N-octadecylmorpholine (N-cocomorpholine);triethylamine; tributylamine; trioctyamine; N, N,N,Ntetramethylethylenediamine; N,N,N,N' tetramethyl-l,3-butane diamine;triethanolamine; N,N-dimethylethanolamine; triisopropanolamine;N-methyldiethanol amine; bis (Z-dimethylaminoethyl) ether;hexadecyldimethylamine; N,N-dimethylbenzylamine; trimethylamine;triethylenediamine (i.e., 1,4 diazabicyclo-[2.2.2]-octane); the formateand other salts of triethylenediamine; oxyalkylene adducts of the aminogroups of primary and secondary amines and other such amine catalystswhich are well known in the art of flexible polyurethane foampreparation. Although metal-containing catalysts such as stannousoctoate are usually employed in the preparation of flexible polyetherurethane foam, such metal catalysts are not preferred in the manufactureof flexible polyester foam.

It is to be understood that the aforesaid amines may be used asessentially the sole amine catalyst of the reaction mixtures employed inthis invention or any combination of two or more such amines may beemployed. The amine catalyst may also be introduced into the reactionmixture in the form of a solvent solution containing from about 10 toabout 80 weight percent of total active catalyst. Suitable carriersolvents of amine catalysts include water-soluble glycols such asdiethylene glycol; dipropylene glycol; and 2-methyl-2,4-pentanediol(hexylene glycol).

The catalyst may also be used in combination with other additives suchas any of the non ionic organic surfactants described above inconnection with the solution compositions of this invention. Examples ofnon ionics which are especially useful as components of the catalystsolutions are the oxyethylated nonylphenol compounds represented by thegeneral formula wherein k is a number having an average value of fromabout 9 up to about or more, including average values of k which areeither whole or fractional numbers such as 9, 10.5, 15 and the like.When used, the non ionic organic surfactant may be present in an amountfrom about 10 to about 80 weight percent, based on the total weight ofthe catalyst solution. The catalyst solution may also include minoramounts of polysiloxane-polyoxyalkylene block copolymers and/or theorganosilicone polymers of this invention.

It is to be understood that any of the aforesaid amine catalysts orsolutions thereof can be added directly to the foam-producing reactionmixture or they can be added in premixed form with water and thepolymeric organosilicone foam stabilizers of this invention. In thelatter event, the catalyst is preferably added as a component of theabove-described homogeneous aqueous premixtures of this invention.

The amine catalyst is present in the final foam-producing reactionmixture in an amount of from about 0.2 to about 8 parts by weight ofactive catalyst (that is, the amine exclusive of other componentspresent in solutions thereof) per 100 parts by weight of the polyesterpolyol reactant.

Foaming can be accomplished by employing a minor amount of apolyurethane blowing agent such as water, in the reaction mixture, thereaction of water and isocyanate generating carbon dioxide blowingagent, or through the use of blowing agents which are vaporized by theexotherm of the reaction, or by a combination of the two methods. Thesevarious methods are known in the art. Thus, in addition to or in placeof water, other blowing agents which can be employed in the process ofthis invention include methylene chloride, liquefied gases which haveboiling points below 80 F. and above F., or other inert gases such asnitrogen, carbon dioxide added as such, methane, helium and argon.Suitable liquefied gases include aliphatic and cycloaliphaticfluorocarbons which vaporize at or below the temperature of the foamingmass. Such gases are at least partially fluorinated and may also beotherwse halogenated. Fluorocarbon blowing agents suitable for use infoaming the formulations of this invention includetrichloromonofluoromethane, dichlorodifluoromethane,1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2-fluoro 3,3difluoro-4,4,4-trifluorobutane, hexafluorocyclobutene andoctafiuorocyclobutane. Another useful class of blowing agents includethermally-unstable compounds which liberate gases upon heating, such asN,N-dimethyl-N,N'-dinitrosoterephthalamide, and the like. The generallypreferred method of foaming for producing flexible foams is the use ofwater or a combination of water plus a fluorocarbon blowing agent suchas trichloromonofluoromethane.

The amount of blowing agent employed in the foaming reaction will varywith factors such as the density that is desired in the foamed product.Usually, however, from about 1 to about 30 parts by weight of theblowing agent per 100 parts by weight of the polyester polyol startingmaterial is preferred.

The organic flame retardants that can be employed in producingflame-retarded flexible polyester foams in accordance with the teachingsof this invention can be chemically combined in one of the other of thematerials used (e.g., in the polyester polyol), or can be discretechemical compounds added as such to the foam formulation. Theflame-retardants preferably contain phosphorus or halogen, or bothphosphorus and halogen. Flame-retardants of the discrete chemicalcompound variety include: 2,2-di(bromoethyl)-1,3-propanediol; tris-2-chloroethyl) phosphate [ClCH CH O) P(O) 2,3-dibromopropanol;brominated phthalate ester diols (e.g., from tetrabromophthalicanhydride and propylene oxide); oxypropylated phosphoric acid; polyolphosphites [e.g., tris(dipropylene glyCOl)ph0sphite]; polyolphosphonates [e.g., bis(dipropylene glycol) hydroxymethane phosphonate];tris(2,3-dibromopropyl) phosphate; tris( l,3-dichloropropyl)phosphate;tetrabromobisphenol-A; tetrabromophthalic anhydride; tetrachlorophthalicanhydride; chlorendic acid and its anhydride; dially chlorendate; 2,4,6-tribromophenol; pentabromophenol; bis(2,3-dibromopropyl)phosphoric acidor salts thereof; tris(l-brorno-3- chloroisopropyl)phosphate; brominatedanilines and dianilines; diethyl N,N bis(Z-hydroxyethyl)aminomethylphosphonate; di'poly(0xyethylene) hydroxymethyl phosphonate; 0,0-diethylN,N bis(2-hydroxyethyl)aminomethyl phosphonate; di-poly(oxypropylene)phenyl phosphonate; di-poly(oxypropylene) chloromethyl phosphonate;di-poly(oxyproylene) butyl phosphate; and other flame retardants knownto the art. The aforesaid compounds may be used as essentially the soleflame retardant or various combinations thereof may be used.

Those of the above flame-retardants of the discrete chemical compoundvariety which contain groups reactive with hydroxy or isocyanato groupscan be used as reactants in producing the polyester polyols or can bereacted with organic polyisocyanates to produce modified polyols orpolyisocyanates having chemically combined flameretardant groups. Suchmodified polyester and polyisocyanates are useful as reactants in theprocess of this invention. In such cases, due regard must be given tothe possible effect of the functionality of the compound on the otherproperties (e.g., degree of flexibility) of the resulting foam.

The flame retardant can be used in an amount from about 1 to about 25parts by weight per parts by weight of the polyester polyol reactant.

Other additional ingredients can be employed in minor amounts inproducing polyester urethane foams in accordance with the process ofthis invention, if desired, for specific purposes. Thus the aforesaidinhibitors such as Ionol (which can also be added as components of theaqueous premixed solutions of this invention) can be added directly tothe final foam formulations. Similarly, hexylene glycol can be added tothe final formulation as a compression set additive, although it canalso be introduced as a component of the solution compositions of thisinvention. Paraffin oil can be added to regulate cell structure so as tocoarsen cells and thereby reduce the tendency of the foam to split.Other additives that can be employed are dyes or pigments andanti-yellowing agents.

The process described herein for the production of flexible polyesterurethane foam, can be carried out in accordance with the prepolymertechnique in accordance with which the polyester polyol andpolyisocyanate are prereacted such that a substantial amount ofunreacted isocyanate groups remain. The resulting prepolymer is thencombined with the foam stabilizers of this invention, amine catalyst andblowing agent. Usually, however, the process is carried out as aone-shot process in which the polyester polyol and polyisocyanatereactants are independently added to the foam-producing reactionmixture. The foaming and urethane-forming reactions occur without theapplication of external heat. Often the resulting foam is cured byheating the foam at a temperature between about 100 C. and about C. forabout 10 to about 60 minutes to eliminate any surface tackiness, asdesired. It is to be understood that variations in process conditionsand manipulative steps can be used as known in the art. For example, thevarious ingredients of the reaction mixture can be combined and thefoaming reaction mixture poured into a mold, or the various ingredientscan be combined and the foaming reaction mixture commenced and completedin a mold.

The relative amounts of the various components reacted in accordancewith the above-described process for producing flexible polyesterurethane foams are not narrowly critical. The polyester polyol andpolyisocyanate are present in the foam-producing formulation in a majoramount. The relative amounts of these two components is the amountrequired to produce the urethane structure of the foam and such relativeamounts are well known in the art. The source of the blowing action suchas water, auxiliary 'blowing agents, amine catalyst and theorganosilicone polymeric foam stabilizers are each present in a minoramount necessary to achieve the function of the component. Thus, theblowing agent is present in a minor amount suflicient to foam thereaction mixture, the amine catalyst is present in a catalytic amount(i.e., an amount sufiicient to catalyze the reaction to produce themethane at a reasonable rate), and the organosilicone polymers of thisinvention are present in a foam-stabilizing amount, that is, in anamount sufficient to stabilize the foam. The preferred amounts of thesevarious components are a given hereinabove.

The flexible polyester urethane foams produced in accordance with thisinvention can be used in the same areas as conventional flexiblepolyester urethane foams. For example, they can be used as textileinterliners, cushioning materials for seating and for packaging delicateobjects, and as gasketing materials.

The following examples are offered as illustrative of the presentinvention and are not to be construed as limitative.

Molecular weights given in the examples for various polymer compositionsof this invention, were measured by Gel Permeation Chromatography(abbreviated in the examples as G.P.C.) using a calibration curveshowing the relationship between the respective elution volumesestablished for dimethylsiloxane fluids of different molecular weightsand the respective known molecular weights of such fluids. Inestablishing the calibration curve, the various dimethylsiloxane fluidswere in solution in trichloroethylene solvent. In measuring themolecular weights of the polymers described herein, the elution volumeobserved for any particular polymer product (in trichloroethylenesolvent) was equated with the corresponding elution volume of thecalibration curve, and the molecular weight associated with thatparticular elution volume was assigned as the molecular weight of thepolymer product. The use of Gel Permeation Chromatography for measuringmolecular weights is discussed in Polymer Fractionation (ed. Manfred I.R. Cantow, Academic Press, Inc. New York 1967), pages 123-173, ChapterB4, entitled, Gel Permeation Chromatography, by K. H. Altgelt and J. C.Moore.

The following Examples 1 and 2 illustrate the preparation of polymers ofthis invention containing and (CH SiO' units, which polymers aredesignated herein as lSurfactants A and B, respectively.

EXAMPLE 1 (a) Preparation of The allyl end-blocked polyether having anaverage molecular weight of about 389 and the average composition CH=CHCH (OC H OCH was mixed in an amount of 1200 grams (3.1 mols) with 600ml. of toluene and parts per million (p.p.m.) of Pt as H PtCl in around-bottom flask equipped with a reflux condenser, stirrer andthermometer. The mixture was heated to 60 C. and while at thattemperature, about 3 mols (345.15 grams) of methyldichlorosilane[H-Si(CH )(Cl) was added to the mixture at such a rate to maintain thetemperature at about 8596 C. After completion of the reaction andremoval of toluene solvent by rotary 26 evaporation, 1540 grams ofproduct was provided. The reaction product has the average formula,

CH O(C H O) -C H Si(CH )Cl (b) Preparation of Surfactant A The apparatusemployed in this example comprised a 3-necked reaction flask equippedwith a mechanical stirrer, distilling column (vacuum-jacketstrip-silvered; effective length 60 cm.; Helices packing inch ID.) withtake-01f head and thermometer. The reaction flask contained a mixture oftrimethylchlorosilane (54.25 grams; 0.5 mol), tetraethoxysilane (93.7grams, 0.45 mol), CH O(C H O) C H Si(CH )C1 252.0 grams; 0.5 mol)prepared in accordance with paragraph (a) above, and 500 ml. of toluene.Water was added to this mixture in an amount of 59.6 grams (about 100percent excess over stoichiometry) without applying external heat. Thereaction was exothermic. After the completion of water addition, thereaction mixture was allowed to stir for about 2 hours at ambienttemperature. After this period of time, the mixture was heated andvolatiles (ethanolwater-HCl-toluene) were removed (boiling range 70-C.), followed by the removal of excess water at C. The reaction mixturewas further heated to reach the reflux temperature of toluene C. at thehead) and was kept at this point for several minutes. The reactionmixture was then cooled, neutralized with sodium bicarbonate andfiltered. After further removal of toluene by rotary evaporation at 50C. and 1 mm. mercury pressure, the reaction product weighed 250 grams(83 weight percent yield, based on complete hydrolysis). Analysis of theproduct showed the presence of residual OH and OC H (0.8 and 1.6 weightpercent, respectively). Based on the relative molar proportions ofreactants employed, the mole ratio (azbzc) of the monomeric units in theliquid polymer product (designated herein as Surfactant A) is 0.92121.

EXAMPLE 2 Preparation of Surfactant B The reaction of this example wascarried out in a reaction vessel equipped with a thermometer, condenserwith take-off head, and stirrer. The reaction mixture contained 400 ml.of xylene, 0.5 mol of each of trimethylchlorosilane (54.25 grams) and CHO-(C H O C H ,-Si (CH C1 (252.0 grams) prepared as described inaccordance with Example 1(a) above, and 0.8 mole of tetraethoxysilane(167.0 grams). While stirring this mixture, water (37.8 grams) wasslowly added thereto, followed by stirring of the reaction mixture for 4hours at ambient temperature. After removal of volatiles below 101 C.,filtration and solvent removal, 302.0 grams of liquid polymer productwas obtained. The product has a molecular weight of about 4300 (G.P.C.)and residual OH and OC H contents of 1.2 and 2.1 weight percent,respectively. Based on the relative molar proportions of reactants, themole ratio (azbzc) of the S104/2:CH O-(CzH4O)1.:CaHsS10m:(CH SlO g unitsin the liquid polymer product (designated herein as Surfactant B) is1.61121.

The following Examples 3-9 illustrate the preparation of polymerscontaining Si0 i CQH5CH20'-'(C2H40)6,C3H6-SiO2/2 and (CH Si01l2 units,designated herein as Surfactants C through H and J, respectively. In thepreparation of these surfactants, the polyether-substitutedmethyldichlorosilane reactants EXAMPLE 3 28 EXAMPLE 8 Preparation ofSurfactant H The reaction of this example was carried out in a recationvessel equipped with a thermometer, condenser 5 Preparaflon f 6 2 2 4)s.s with take-off head, and stirrer. The reaction mixture cona s s) 2tained 3000 ml. of xylene, and about 4 moles of each of Following theprocedure of Example 1(a) above, 438 mmethylchlorosllane (432 grams)grams (1 mole) of the allyl end-blocked, benzyl-capped C H CH C H O H SiCH c1 polyether having a molecular weight of about 438 and 6 5 2 2 4 33) 2 the average composition, (2212 grams) and tetraethoxysilane (832grams). While stirring this mixture, water was slowly added thereto inan CH2 CHCH2 (OCH2CH2)M OC.H2C6H5 amount of 324 grams. After the wateraddition was com- (capping about 95 percent) was reacted in 200 ml. ofpleted, the reaction mixture was stirred at ambient temtoluene solventwith methyldichlorosilane (115 grams; 1 perature f several h Th mixturewas th h t d mole) in the presence of 10 ppm. of Pt as H PtCl R8- andvolatiles (ethanol-water-HCl-xylene) were removed moval of toluenesolvent provided 550 grams of addition (boiling range of 70-95 C.). Thereaction mixture was product having the average composition, thencooled, neutralized with sodium bicarbonate and filtered. Removal ofxylene by rotary evaporation afc6H5CH2O (cal-14.0) C3H 1(CH3)C12 fordedthe product (2460 grams). Analysis of the product Pr paration ofSurfactant C showed a silicon content of 11.0 weight percent (calcu Thereaction of this example was carried out in essenlated SIZE-1%) and thePresfiinCe resldual OH and tially the same manner as in Example 2 exceptthat: the 'T Contents of and Welght Percent respec reaction mixturecontained 200 ml. of xylene and 0.25 nvely- The molecular weight of FProduct was mol of each of trimethylchlorosilane (27 12 grams), 3900.Based on the relative molar porportions of reactants employed, the 810 CH CH O-( CgH O C H St(CH C12 CH (138.8 grams) prepared in accordancewith Example 3(a) CH5CH20 (CIHO)M C,HG Siomand (CHmsiOm andtetraethoxysilane (52 grams); and the amount of 30 water added theretowas 38 grams. Analysis of the liquid monomeflc umts present In the hqufdPolymer Prod product (148 grams) showed the presence of residual uct@eslgnatefd surfagtant H) P Equlmolar and OC2H5 contents of L1 and 025weight portions that 1s (the a.b.crat1o is about 1.1.1). cent,respectively. Based on the relative molar proportions EXAMPLE 9 ofreactants employed, the mole ratlo (zlibzc) of the Preparation ofSurfactant J p a The reaction of this example was carried out inessentially the same manner as in Example 8 above, except 3)3 1/2 unitsin h P y p ct (d slgnate that: the recation mixture contained 300 ml. ofxylene, herein as Surfactant C) 1s l:l:l. 40 0.5 mol of eachtrimethylchlorosilane (54.25 grams) and EXAMPLES 4-7 C H CH O-( C H O) 6C H,,-Si CH C1 In accordance with these examples, four additional (276.5grams), and 0.45 mol of tetraethoxysilane (93.7 polymers were prepared,designated herein as Surfactants grams); and the amount of Water addedthereto was D, E, F and G, using the reactants and amounts thereof 59.5grams percent excess over stochiometry). as set forth in the followingTable I. In Examples 4, 6 Analysis of the product (285.5 grams) showedthe presand 7, 200 ml. of xylene was used as solvent, the reaction enceof residual --OH and OC H in amounts of 1.2 mixture of Example 5containing 400 ml. of xylene. The and 0.1, respectively. Based on therelative proportions respective procedures were essentially as describedunder of reactants, the mole ratio of SiO :C H CH O Example 2 above. Therelative proportions of the mono- 5O CH3 meric units contained in therespective liquid polymer products are expressed in Table I by theratio, (azbzc). (CHOM'PCHPMOHZ(CHQ'SIOM TABLE I Example Surfactant D E FG Reactants Si(OCzH5)4I Grams 5. 20 167 31. 23 52.0 Mols O. 25 0. 8 0.15 0. 25

(2H3 CaHsCHzO-(CzH40)B-sCaHs-SiCla 27. 12 54. 25 27. 12 43. 35 Mols 0.25 0. 5 0. 25 0. 4 Water, grams (rnl.) 38 40. 0 (40) (40) Polymerproduct:

Weight, grams 149 308 152 ResidualOH, weight percent; 0.9 12.5 1.17Residual O C2H5, weight percent 3. O 0. 14 0. 14 Molecular weight(G.P.C.) 6.000 3,300 Moleratio oiunits,a:b:c 1.6:1:1 0.6:1:1 1 121.6

1 Designates the mole ratio of 8104/2:

| CuHsCHzO- (CzH40)u.t-C3HaS log/a: (CH3); 310 /2, respectively based onthe relative molar proportions of reactants.

29 units in the liquid polymer product (designated herein as SurfactantI) is 0.9:121.

EXAMPLES 10-13 Preparation of Surfactants K, L, M and N In accordancewith these examples, four additional polymers of this invention,designated herein as Surfactants K, L, M and N, were prepared using thereactants and amounts thereof as set forth in the following Table II.The cohydrolysis-cocondensation reaction of Example 10 was carried outin toulene solvent in substantially the same manner described forExample 1(b). The reactions of Examples 11-13 were carried out inxylene. The clear liquid polymer product of Example 10 (Surfactant K),was found to contain 11.1 weight percent silicon and 0.4 weight percentresidual toluene, and has a viscosity of 271 centistokes at 25 C. Therespective molecular weights (G.P.C.), residual silicon-bonded hydroxyland ethoxy contents and the relative molar proportions (expressed as theazbzc ratio) of the monomeric units contained in Surfactants K through Nare indicated in the following Table H.

TABLE II Example ducing reaction mixture, designated herein as FoamFormulation A, which had the following composition:

TABLE IIIFOAM FORMULATION A The polyester polyol employed was acommercially available polyester resin produced from adipic acid,diethylene glycol and trimethylol propane in a mole ratio ofapproximately 1:1:0.2. This polyester has a hydroxyl number of about 50to 56, a molecular weight of about 2,000, an acid number not greaterthan 2 and a viscosity of about 17,000 centistokes at about C. Thisparticular polyester is sold under the name Witco Fomrez No. 50.

2 This component was a mixture of 2,4-tolylene diisocyanate (80 weightper cent) and 2,6-tolylene diisocyanate. Index 105 means that the amountof mixture employed was 105 percent of the stolchiometric amountrequired to react with the polyester polyol and water present in thefoam formulation.

Polymer product:

Resi ual OH.... CaHs. Molecular weight (G.P. Mole ratio of units, azbzc1 Designates the mole ratio of SiOila:

ov-nop- CeHsCHzO-(CzH O) d-CsHc-SiOz/z: (CH3)! 310 /1,

respectively, based on the relative molar proportions of reactants.

EXAMPLE 14 Preparation of Surfactant O In accordance with this example,grams of Surfactant D identified in Table I above, was dissolved in 80ml. of toluene in a nitrogen atmosphere. To this mixture, 0.3 grams ofN-ethylmorpholine was added, followed by the addition of 5 grams ofmethyl isocyanate. The reaction mixture was heated at 6070 C. for 2hours under nitrogen followed by cooling and solvent removal by rotaryevaporation. The liquid product (designated herein as Surfactant 0) hada molecular weight (G.P.C.) of 7100 and, upon analysis, was found tocontain 10.3 weight percent silicon (calculated Si=13.1 weight percent)and residual OH and OC H contents of about 1 and 0.2 weight percent,respectively.

EXAMPLE 15 Preparation of Surfactant P In accordance with this example,30 grams of Surfactant E identified in Table I above, was dissolved in80 ml. of toluene and treated with 0.3 gram of N-ethylmorpholine and 5grams of methyl isocyanate, following the procedure of Example 14. Theliquid product (designated herein as Surfactant P) had a molecularweight (G.P.C.) of 7200 and, upon analysis, was found to contain 0.7 and1.1 weight percent of residual OH and OC H groups, respectively.

In the following Examples 16-30, foams were produced using theabove-described Surfactants A through H and I through P of the presentinvention as the respective foam-stahilivinr surfactant component of thefoam-pro- The results of Examples 16-30 were carried out in accordancewith substantially the same general procedure which entailed thefollowing steps. The surfactant, amine catalysts and water were premixedin a 50 milliliter beaker. The polyester polyol reactant was weighedinto a tared 32-ounce capacity container. The flame-retardant [tris(2-chloroethyl)phosphate] and tolylene diisocyanate reactant were alsoweighed into the container and mixed with a spatula until homogeneous.Further mixing was done on a drill press equipped with a doublethree-bladed marinetype propellor about three inches in diameter. Themixing in the drill press was accomplished at 1000 revolutions perminute for eight seconds. Then the premixture of surfactant, catalystand water was added and mixing was continued for seven additionalseconds. The reaction mixture was poured into a 12 in. x 12 in. x 12 in.cardboard box, was allowed to rise and was then cured for about 30minutes at C. In most instances, samples were prepared for breathabilitymeasurements and for a determination of burning resistance (burningextent and flame rating) in accordance with ASTM 1692-59T.

The following terms are used to describe the quality of the foamsproduced in the examples:

Rise denotes the foam height and is directly proportional to potency ofthe surfactant.

Breathability denotes the porosity of a foam, being roughly proportionalto the number of open cells in a foam, and was measured in accordancewith the NOPCO breathability test procedure described by R. E. Jones andG. Fesman, Journal of Cellular Plastics, January, 1965. In accordancewith this test, breathability is measured as follows: A 2 inch x 2 inchx 1 inch piece of foam is cut from near the center of the bun. Using aNopco Foam Breathability Tester, Type G. P.-2 Model 40 G. D. 10,

31 air is drawn through the one inch portion at a pressure differentialof 0.5 inches of Water less than atmospheric pressure. The air flow isparallel to direction of original foam rise. The degree of openness ofthe foam (or foam breathability) is measured by air flow and isexpressed as standard cubic feet per minute (SCFM) Burning Extentdenotes the burned length of a test specimen of foam as measured inaccordance with standard test procedure ASTM 1692-591.

SE indicates that, on the basis of the results obtained in the aforesaidASTM 1692-59T test, the foam is rated as self-extinguishing.

EXAMPLES 16-17 The surfactants employed in these examples were theabove-described Surfactants A and B in which the respective mole ratiosof the SiO 32 The results of Table IV indicate that Surfactants A and Bof this invention have a good combination of potency and processinglatitude as stabilizers f flexible polyester foam and, in addition,possess the further desirable property of allowing for the formation ofself-extinguishing flame-retarded foams.

EXAMPLES 18-26 TABLE V Stability of flexible polyester foaming usingsuralcitants containing 5104/1,

C and (CHa)aSlO1/z units in a mole ratio of azbzcz, respectively, asdefined below Surfactant Parts by Foam properties wt. in

foam Breath- Burning Example Desigformula- Rise ability extent Flame No.nation a:b.c tion A (inches) (s.c.f.m.) (inches) rating C 1 :1 0. 35 5.7 2 SE C '1 0.5 5. 8 2. 1 SE C 1 1. 0 5. 8 3. 0 SE F 1 1 0.35 5. 7 1. 1SE F 1 0.5 5. 7 1. 5 SE F 1 1. 0 5. 7 1. 5 SE G 1 6 0.35 5. 6 1. 5 SE G6 0. 5 5. 7 1. 6 SE G 6 1. 0 5. 7 1. 9 SE 11 :1 0.35 5.9 1.6 SE H :1 0.5 5. 8 2. 4 SE H :1 1.0 5. 8 2. 8 SE J :1 0.35 5.8 1.3 SE J :l 0. 5 5.8 1. 7 SE J :l 1. 0 5. 9 2. 2 SE K :1 0.35 5.8 1.3 SE K 1 0. 5 5. 8 1. 7SE K 1 1. 0 5. 9 2. 1 SE L l 1 0. 5.6

1 Average value of d in polyether chain is 6. 2 Average value of d inpolyether chain is 8. Average value of d in polyether chain is 8.

and (CH SiO units are 0.9:1:1 and 1.6:lz1, respectively. Thebreathability and burning extent of foams produced using these polymersin Foam Formulation A of Table III above, were measured at threedifferent polymer concentrations. The amount of surfactant employed andthe results are as follows:

The results of Table V indicate that Surfactants C, F, G, H and Ithrough N of this invention were effective stabilizers of flexiblepolyester urethane foam as indicated by foam rise. Although SurfactantsL, M and N had overall good potency as stabilizers and provided usefulfoams, the foamed products produced therewith tended to be tightindicating close celled foams, or coarse indicating foams having fewercells (about 25 or less) per linear inch. Of these various surfactants,the best overall combination of properties was exhibited by SurfactantsC, F, G, H, J and K in which the respective mole ratios (azbzc) ofmonomeric units are Within the preferred range expressed herein, thatis, about 0.61.8:1:0.8l.8 and the ratio of a+c:b is l.42.8: 1. As shownby the data of Table V, these preferred surfactants provided more Openfoams than Surfactants L, M and N, as indicated by the breathabilitymeasurements.

33 EXAMPLES 27-28 The surfactants employed in these examples wereSurfactant D (prepared as described in Example 4) in which the 8104 3,

and (CH SiO monomeric units were present in equimolar proportions, andSurfactant O which is the polymer product obtained by treatment ofSurfactant D with methyl isocyanate as described in Example 14. Thebreathability and burning extent of foams produced using these polymersas the foam stabilizing surfactant of Foam Formulation A of Table IIIabove, were measured at three different polymer concentrations. Theamount of surfactant employed and the results are given in Table VIwhich also indicates the residual hydroxyl and ethoxy contents of eachsurfactant.

TABLE VI Example No.

Surfactant D O OH, wt. percent--. 1. 5 1. 5 1. 5 1 1 1 02H wt. percent3. 3. 5 3. 5 0. 2 0. 2 0. 2 Parts by Wt 0. 35 0. 5 1. 0 0. 35 0. 5 1. 0Rise. inches 5. 8 5. 7 5. 8 5. 8 5. 9 5. 9 Breathability, s.c.f.m 1.8 1. 9 2. 3 2. 4 2. 8 3. 7 Burning extent, inches- 2 2. 1 2. 1 1. 4 1. 62. 6 Flame rating Self-extinguishing EXAMPLES 29-30 The surfactantsemployed in these examples were Surfactant E (prepared as described inExample 5) in which the TABLE VII Example No.

Surfactant. E P

-0H, wt. percent..--. 0. 9 0. 9 0.7 0. 7 0.0 0 02H wt. percent 3. 0 3.O 1. 1 1. 1 1. 7 Parts by Wt... 0. 50 1.0 0.35 0.5 1.1 Rise, inches 5. 85. 8 5. 7 5. 7 5. 8 5. 7 Breathability, s.c.t'.m 1. 5 1. 2 1. 5 2. 6 2.8 3. 5 Burning extent, inches... 1. 2 1. 8 1. 9 1. 3 1. 4 1. 5 Flamerating Self-extinguishing The data of Tables VI and VII show that ineach instance Surfactants D and E and their respective methyl isocyanatederivatives were potent stabilizers of flexible polyester foam andprovided good quality self-extinguishing foam. The data also show thatthe treatment of Surfactants D and E with methyl isocyanatesubstantially reduced the total content of residual hydroxyl and ethoxygroups, and that the methyl isocyanate derivatives provided more openfoams as evidenced by increased breathability, without sacrifice of lowburning extent.

34 EXAMPLES 31-37 In these examples, a potency determination was made ofsurfactants of this invention using a foam formulation, designated asFoam Formulation B, which contained 5 parts by weight of water per partsby weight of polyester polyol reactant. The 5 parts water system isusually more diflicult to stabilize than the more conventionalformulations containing less water and thus provides a relativelysensitive test of potency. The composition of Foam Formulation B is asfollows:

TABLE VIIIF OAM FORMULATION B Component: Parts by weight SurfactantVaried (0.35 and 1). Polyester polyol 1 100.0. N-ethylmorpholine 1.9.Hexadecyldimethylamine 0.3. Water 5.0. Tolylene diisocyanate (Index 1The polyol employed was the same as that of Foam Formulation A and isidentified in footnote 1 of Table II.

The isocyanate employed was the same as that of Foam Formulation A andis identified in footnote 2 of Table III. Each of Examples 31-37includes two foaming reactions (indicated as -1 and -2) which werecarried out at different concentrations of surfactants using the generalprocedure described above with reference to Examples 16-30. The moleratio (azbzc) of the monomeric units of Surfactants B, D-G, J and Kemployed in these examples and the results are given in the followingTable IX.

TABLE 1X gtgbilization of flexible polyester foam using surfactantscontaining 1 ill,

R0( C3H40)d 'C3H6' siO2II and (CHmSiOm units in a mole ratio of u:b:c,respectively, wherein R- is methyl (Surfactant B) or benzyl (SurfactantsD-G, J and K), and a:b:c is defined below Parts by wt. in foam Sur-Formu- Rise Cell Example factant a:b:c lation B (inches) structure 1. 6:1:1. 0. 35 9. 1 Excellent. 1. 6: l: 1 1 9. 1 Do. 1.6:1:1 0.35 9.2 Do. 1.6: 1:1 1 9. 3 D0. 1:1:1 0.35 9.1 Do. 1:1:1 1 9. 1 D0. 121:1. 6 0. 35 9.0Good. 121:1. 6 1 9. 0 Do. 0. 9: 1:1 0. 35 9.3 Excellent. 0. 9:1:1 1 9. 4Do. 0.92121 0.35 9.3 Do. 0. 9: 1: 1 1 9. 4 D0 0. 6:1:1 0. 35 8. 7 Coarse0. 6:1:1 1 8. 9 Do.

EXAMPLES 38-44 In accordance with these examples, Surfactant H andSurfactant K were blended wtih various organic compounds to provideillustrative solution compositions of this invention. These blendedcompositions are designated herein as Surfactants Q through W and eachwas used as the surfactant component of Foam Formulation A of Table IIIabove in a concentration of 1 part by weight, following the generalprocedure described above with reference to Examples 16-30. In using theblended surfactants, clear, homogeneous aqueous premixtures wereobtained when the water and amine catalysts of Foam Formulation A werecombined therewith. The composition of the blended surfactants and theresults of thes examples are given in the following Table X.

TABLE X Foam properties Blended surfactant Breath- Burning Example Wt.percent of Rise ability extent Flame No. No. Components components 1(inches) (s.c.f.m (inches) rating 38 Q, Surfactant H 45. 6 (46,1) 5. 92. 3 1. 6 SE a 53%;; exy ene g yco 39 R Surfactant 54. 5. 8 2. 2 l. 4 SETall oil 23.0 Hexylene glycol. 23. 0 40....; 8 Surfactant H 45. 6(46. 1) 5. a 2. 7 1. BE

Tall oil 20. 0 (20. 2) Hexylene glycol., 20.0 (20.2) Anionic surfactant13. 3 (13. 5) 41..:::....-. T Surfactant K 50 5. 8 2. 6 1. 0 SE Tall oil12. 5 Hexylene glycol. 37. 5 42..- U Surfactant K.. 50.0 5. 8 2. 6 1. 4SE Tall oil 15. 0 Organic non 35.0 Surfactant 43 V Surfactant K v0.0 5.8 2. 4 l. 5 SE Tall oil 15. 0 Organic non ionic. 35.0 Surfactant 4 l 44W Surfactant K 52.0 5. 8 2. 4 1. 5 SE Tall oil 15.6 Hexylene glycol. 21.0 Organic non ionic. 10. 4 Surfactant Ionol" 1. 0

1 Figures in parenthesis are normalized on the basis of 100 percent. 1Diethylamine salt of C -alkylated aromatic sulfonic acid.

I 2,6-di-tertiary-butyl-p-crescl.

The results of Table X demonstrate that the solution compositions of theorg-anosilicone polymers of this invention also possess good potency asstabilizers of flexible polyester foam and allow for the formation ofselfextinguishing foams.

A blended surfactant composition, designated herein as Surfactant I,comprising a p0lyoxyalkylenepolysiloxane block copolymer in combinationwith an anionic organic surfactant, was also tested under the conditionsemployed in the examples of Table X. In this test, Surfactant I which isnot a composition of the present invention, was used as the surfactantcomponent of Foam Formulation A in a concentration of 1 part by weightper 100 parts of the polyester polyol reactant, following substantiallythe same general procedure described above with reference to Examples16-30. The composition of Surfactant I which is used commercially forthe manufacture of flexible polyester urethane foam, and the resultsobtained therewith are given in Table XI (wherein Me designates a methylgroup).

1 Not a surfactant of this invention.

2 Typical analysis (welght percent) 62.0 sodium sulfonate, 32.7 mineraloil, 4.5 water, 0.7 inorganic salt; average molecular weight (ofsulfonate portion) is 435; flash point, 0.0.0.,

400 F.; sold commercially under the name Bryton 430."

2500 parts per million parts of components (a) to (d).

Results Rise, inches 5.8 Breathability, SCFM 2.6 Burning extent, inches5.0

Flame Rating ,t Burns The results of Tables X and XI show that, Whereasthe foams produced using the solution compositions of this invention(Surfactants Q through W) had burning extents sufiiciently low to berated as self-extinguishing, the foam produced using Surfactant I didnot qualify as self-extinguishing.

In the runs summarized in the following Table XII, other polymersdesignated herein as Polymers II, III and IV, which are not within thescope of the present invention, were used as the surfactant component ofFoam Formulation A of Table III above. These polymers are identified asfollows:

Polymer II contains SiO units and the two types of monofunctional units,(CH SiO and in a mole ratio of 1.6:l:l, respectively; the mole ratio ofSiO total monofunctional units, normalized on the basis of one mole ofSiO is 1:1.25.

Polymer III contains SiO and (CH SiO units in a mole ratio of 1:1 andwas used as a 50 weight percent solution in xylene.

Polymer IV is a commercially available product designed for use in themanufacture of polyvinyl chloride foams. It is supplied in about a 50weight percent solution in xylene having a viscosity of 6 centistokes at77 F. and a specific gravity of 1.00 at 77 F. On the basis of analyticaldata, it is believed that this polymer contains SiO and (CH SiO units ina mole ratio of 1:0.8, respectively.

The runs of Table XII were carried out following the general proceduredescribed above with specific reference to Examples 16-30 and includecontrol runs based on the use of the above-described Surfactant K ofthis invention. The concentration of Surfactant K and of Polymers II,III and IV employed in each run is also given in Table XII.

TABLE XII Parts by weight in foam Breath- Formu- Rise ability RunSurfactant lation A (inches) (s.c.f.m.) Remarks Control-1 K 1 0.35 5.82. 1 Excellent foam. 1 Polymer II 2 0.35 Shrunk..- None Severeshrinkage. Control-2-. 1 5.9 6 Excellent cell structure. 2--. PolymerIII 3 1 Boiled 3..- Polymer* IV 4 6 1 Collapsed E 1SlO4/2ICaH5CHzO-(CzH4O)ans-CaHs-SiO2/22(CHa)aSiQ1/2=0.9:1:1. 1 SiO/z:[HO-((C2H4O1. O HSi(CH3)zO1/z+( Hs)3S1Oi/2l =1:1.25.

3 S104/2:(CHs)sSiOi/2=1:1; employed as 50 weight percent solution inxylene.

4 SiO /a:(OHa)aSiO1/2 believed to be 1:0.8; employed as 50 weightpercent solution in xylene. Basis, weight of dissolved polymer exclusiveof weight of xylene solvent.

"Not a polymer of this invention.

The results of Table XII show that whereas Surfantaut K of thisinvention provided excellent flexible polyester foam, Polymers II, IIIand IV failed to perform as effective stabilizers.

What is claimed is:

1. A solution composition consisting essentially of four differentcomponents (1), (2), (3) and (4) wherein: component (l) is a liquidorganosilicone polymer containing monomeric units (A), (B) and (C) where(A) is SiO (B) is a difuctional siloxy unit having the formula,

wherein R is an alkyl group having from 1 to 4 carbon atoms, d has anaverage value of from about 5 to about 15, n. has a value of from 2 to4, provided at least 75 percent by weight of the poly(oxyalkylene)chain, -(C,,H O) is constituted of oxyethylene units, m has a value offrom 2 to 4 and W is is a monovalent organic radical selected from thegroup consisting of R RC(O)- and RNHC(O)-- where R is a mono valenthydrocarbon radical having from 1 to 12 carbon atoms, and (C) is themonofunctional siloxy unit,

where R is a lower alkyl group having from 1 to 4 carbon atoms, the moleratio of said (A) to (B) to (C) units being about 0.4:2:1:O.2-2,respectively; component (2) is an organic acidic component consistingessentially of at least one member of the group consisting of aliphaticand cycloaliphatic carboxylic acids having from 15 to 20 carbon atomsand is present in said solution in an amount of from about 5 to about 90parts by weight per 100 parts by weight of said organosilicone polymercontained in said solution; component (3) is a non ionic organicsurfactant; and component (4) is a water soluble glycol, the combinedtotal weight of components (3) and (4) present in said solution rangingfrom about 5 to about 90 parts by weight per 100 parts by weight oforganosilicone polymer contained in the solution.

2. The solution composition of claim 1 wherein said organic acidiccomponent is tall oil.

3. The solution composition of claim 1 wherein said non ionic organicsurfactant is an oxyethylated adduct of at least one alcohol, saidalcohol having from to 18 carbon atoms.

4. The solution composition of claim 1 wherein said non ionic organicsurfactant is an oxyethylated adduct of an alkyl-substituted phenolwherein the alkyl group has from 6 to carbon atoms.

15, n has a value of from 2 to 4, provided at least percent by weight ofthe poly(oxyalkylene) chain,

is constituted of oxyethylene units, m has a value of from 2 to 4 and Ris a monovalent hydrocarbon radical having from 1 to 12 carbon atoms,and (C) is the monofunctional siloxy unit, (CH SiO the mole ratio ofsaid (A) to (B) to (C) units being about 0.4-2:1:0.22, respectively;component (2) is tall oil present in said solution in an amount of fromabout 5 to about parts by weight per parts by weight of saidorganosilicone polymer contained in said solution; component (3) is anon ionic organic surfactant; and component (4) is hexylene glycol, thecombined total weight of components (3) and (4) present in said solutionranging from about 5 to about 90 parts by weight per 100- parts byweight of or ganosilicone polymer contained in the solution.

7. A solution composition as defined in claim 6, wherein R of the saidunit formula of (B) is selected from the group consisting of a loweralkyl group and an arylsubstituted lower alkyl group.

8. A solution composition as defined in claim 7 wherein said lower alkylgroup is methyl.

9. A solution composition as defined in claim 7 wherein saidaryl-substituted lower alkyl group is benzyl.

References Cited UNITED STATES PATENTS 3,594,334 7/1971 Marlin 260-2.5AM 3,655,581 4/1972 Bachura 252356 X 2,855,367 10/1958 Buck 252559 X3,232,880 2/1966 Mausner et al 252529 3,511,788 5/1970 Keil 117-155 R XRICHARD D. LOVERING, Primary Examiner US. Cl. X.R.

252351, 354, Dig. 1; 260-2.5 AH

v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,833,512 Dated September 3, 1974 Inventor(s) Bela Prokai et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 31, immediately before the heading "BACKGROUND OF THEINVENTION" read as a separate paragraph This is a division ofapplication Serial No. 132,534 filed April 8, 1971, now U.S. Pat. No.3,793,360.--. Column 5,

line 17, for "characteristics" read characteristic line 41, for thesymbol E shown within quotation marks read E' Column 7, line 26, for"cappying" read capping Column 8', line 6, for "CHgNHC (O)-" read CH3NHC(0)0- Column 10, line 71, that portion of the formula reading "Si'O"should read Si(0 Column 12, line 58, for "R'3SiO2 2" read R' SiO 2 IColumn 13, line 22, delete this line which reads "shown as thehydrolyzable groups of reactants B and" in its entirety; line 50, for"O.4-2:l:O.2-l" read O.4-2:l:0.2-2 Column 14, line 53, for "repective"read respective Column 15, line 30, for "ally" read allyl Column 16,line 68, for "reactant" read reaction Column 17, line 10, for "arakyl"read aralkyl line 45, for "mixtures" read mixture line 57, for "mitxure"read mixture Column 19 line 33, for "pyrocatehol" read pyrocatechol line63, for "hydroxly" read hydroxyl line 67, "organic analysis" should readORGANIC ANALYSIS Column 21, line 4, for

"cycloalykylene" read cycloalkylene Column 24, line 1, that portion ofthe formula reading "[01" should read [(Cl line 10, for "dially" readdiallyl line 19, for "(oxyproylene)" read (oxypropylene) Column 25, line57, for "(CH3)3SiO2/2" read (CH3)3SiO] /2 line 74, for "96" read 95Columns 2728, Table I, under Example 4, the first numerical entryreading "5.20" should read 52.0 opposite the legend "Residual OH, weightpercent", the third entry reading "12.5" should read 1.25 Column 28,line 39, for "recation" read i FORM P0405" (169) uscoMM-Dc 60376-P69 Iit ILS. GOVERNMENT PRINTING OFFICE i969 0-366-334,

